Adhesive and marking compositions made from interpolymers of ethylene/α-olefins

ABSTRACT

An adhesive composition comprises: (i) at least one ethylene/α-olefin interpolymer, (ii) at least one tackifÊer; and (iii) optionally at least one additive, such as a plasticizer, wax and antioxidant. Preferably, the ethylene/α-olefin interpolymer has a M w /M n  from about 1.7 to about 3.5, at least one melting point, T m , in degrees Celsius, and a density, d, in grams/cubic centimeter, wherein the numerical values of T m  and d correspond to the relationship: T m ≧858.91−1825.3( d )+1112.8( d ) 2 . The composition has relatively higher SAFT temperature and can be used in hot melt adhesives pressure-sensitive adhesives, and thermoplastic marking paints.

FIELD OF THE INVENTION

This invention relates to compositions comprise at least oneethylene/α-olefin interpolymers, methods of making the compositions, andmethods of using the compositions in applications, such as hot meltadhesives, pressure sensitive adhesives, and thermoplastic markingcompositions.

BACKGROUND OF THE INVENTION

An adhesive is a substance capable of holding solid materials (e.g.,adherents or substrates) together by surface attachment. Adhesives havebeen widely used since ancient times. Archaeologists have found evidenceof substances being used as adhesives in Babylon dating back to 4000B.C. and in Egypt between 1500-1000 B.C. The first adhesive patent wasissued in about 1750 in Britain for a glue made from fish. Later,patents were issued for adhesives using natural rubber, animal bones,fish, starch, milk protein or casein. The development of syntheticadhesives from the late 19th century has led to many syntheticadhesives, such as nitrocellulose, phenol-formaldehyde resins,urea-formaldehyde resins, epoxy resins, bismaleimide resins,polysiloxanes, polychloroprene, polyacrylates, polymethacrylates,polyurethanes, polycyanoacrylates, hot melt adhesives and pressuresensitive adhesives.

Pressure sensitive adhesives (PSAs) generally are adhesive materialswhich bond to adherents when a required pressure is applied to effect anadhesion to the adherents. PSAs can be permanent or removable. RemovablePSAs have been widely used in re-positionable applications, such aspost-it notes. Pressure sensitive adhesives are generally based on apolymer, a tackifier and an oil. Some common PSAs are based on polymerssuch as natural rubbers, synthetic rubbers (e.g., styrene-butadienerubber (SBR) and SIS), polyacrylates, polymethacrylates, andpoly-alpha-olefins. The PSAs can be solvent-based, water-based, or hotmelt systems.

Hot-melt adhesives at ambient temperature are generally solid materialsthat can be heated to a melt to hold adherents or substrates togetherupon cooling and solidifying. In some applications, the bondedsubstrates can be detached by remelting the hot melt adhesive if thesubstrates can withstand the heat. The hot melt adhesives can be used inpaper products, packaging materials, laminated wood panels, kitchencountertops, vehicles, tapes, labels, and a variety of disposable goodssuch as disposable diapers, hospital pads, feminine sanitary napkins,and surgical drapes. These hot melt adhesives are generally based on apolymer, tackifier, and a wax. Some common hot melt adhesives are basedon polymer components including ethylene based semi-crystalline polymerssuch as ethylene-vinyl acetate copolymer (EVA) and linear low densitypolyethylene (LLDPE), styrene block copolymers (SBC) such asstyrene-isoprene-styrene (SIS) copolymer and styrene-butadiene-styrene(SBS) copolymer, ethylene ethyl acrylate copolymers (EEA), andpolyurethane reactive adhesives (PUR). One desirable property of hotmelt adhesives is the absence of a liquid carrier, thereby eliminatingthe costly process associated with solvent removal.

Some compositions that contain a polymer, a tackifier and optionally atleast a filler or a pigment may be used as thermoplastic markingcompositions. The polymer can be a silane-modified petroleum resin, anethylene-vinyl acetate copolymer, an atactic polypropylene; acarboxy-modified hydrocarbon resin, an ester-modified hydrocarbon resin,a polyolefin copolymer, or a combination thereof.

Despite the availability of a variety of hot melt adhesives, pressuresensitive adhesives, and road paints, there are still needs for newadhesive compositions with improved properties.

SUMMARY OF INVENTION

The aforementioned needs can be met by various aspects of the invention.In one aspect, the invention relates to adhesive compositions comprisingat least one ethylene/α-olefin interpolymer and a tackifier. In certainembodiments, the ethylene/α-olefin interpolymer has a M_(w)/M_(n) fromabout 1.7 to about 3.5, at least one melting point, T_(m), in degreesCelsius, and a density, d, in grams/cubic centimeter, wherein thenumerical values of T_(m) and d correspond to the relationship:T _(m)>−2002.9+4538.5(d)−2422.2(d)².

In certain embodiments, ethylene/α-olefin interpolymer in the adhesivecompositions provided herein has a M_(w)/M_(n) from about 1.7 to about3.5, and is characterized by a heat of fusion, ΔH in J/g, and a deltaquantity, ΔT, in degrees Celsius defined as the temperature differencebetween the tallest DSC peak and the tallest CRYSTAF peak, wherein thenumerical values of ΔT and ΔH have the following relationships:ΔT>−0.1299(ΔH)+62.81 for ΔH greater than zero and up to 130 J/g,ΔT≧48° C. for ΔH greater than 130 J/g,wherein the CRYSTAF peak is determined using at least 5 percent of thecumulative polymer, and if less than 5 percent of the polymer has anidentifiable CRYSTAF peak, then the CRYSTAF temperature is 30° C.

In certain embodiments, ethylene/α-olefin interpolymer in the adhesivecompositions provided herein is characterized by an elastic recovery,Re, in percent at 300 percent strain and 1 cycle measured with acompression-molded film of the ethylene/α-olefin interpolymer, and adensity, d, in grams/cubic centimeter, wherein the numerical values ofRe and d satisfy the following relationship when ethylene/α-olefininterpolymer is substantially free of a cross-linked phase:Re>1481−1629(d), Re>1491−1629(d), Re>1501−1629(d) or Re>1511−1629(d).

In certain embodiments, ethylene/α-olefin interpolymer in the adhesivecompositions provided herein has a molecular fraction which elutesbetween 40° C. and 130° C. when fractionated using TREF, characterizedin that the fraction has a molar comonomer content of at least 5 percenthigher than that of a comparable random ethylene interpolymer fractioneluting between the same temperatures, wherein said comparable randomethylene interpolymer has the same comonomer(s) and has a melt index,density, and molar comonomer content (based on the whole polymer) within10 percent of that of the ethylene/α-olefin interpolymer.

In certain embodiments, ethylene/α-olefin interpolymer in the adhesivecompositions provided herein has a storage modulus at 25° C., G′(25°C.), and a storage modulus at 100° C., G′(100° C.), wherein the ratio ofG′(25° C.) to G′(100° C.) is in the range of about 1:1 to about 9:1.

In certain embodiments, ethylene/α-olefin interpolymer in the adhesivecompositions provided herein has a molecular fraction which elutesbetween 40° C. and 130° C. when fractionated using TREF, characterizedin that the fraction has a block index of at least 0.5 and up to about1.

In certain embodiments, ethylene/α-olefin interpolymer in the adhesivecompositions provided herein has an average block index greater thanzero and up to about 1.0 and a molecular weight distribution, Mw/Mn,greater than about 1.3.

In certain embodiments, the adhesive composition provided herein is ahot melt adhesive, a pressure sensitive adhesive or a thermoplasticmarking composition.

In certain embodiments, the α-olefin in the ethylene/α-olefininterpolymer is styrene, propylene, 1-butene, 1-hexene, 1-octene,4-methyl-1-pentene, norbornene, 1-decene; 1,5-hexadiene or a combinationthereof.

In certain embodiments, the ethylene/α-olefin interpolymer in thecompositions provided herein has a number average molecular weight,M_(n), of from about 500 to about 500,000.

In certain embodiments, the ethylene/α-olefin interpolymer has a meltindex in the range of about 1 to about 5000 g/10 minutes, about 2 toabout 2000 g/10 minutes or about 5 to about 1500 g/10 minutes measuredaccording to ASTM D-1238, Condition 190° C./2.16 kg. In otherembodiments, the ethylene/α-olefin interpolymer has a melt index in therange of about 0.1 to about 2000 g/10 minutes measured according to ASTMD-1238, Condition 190° C./2.16 kg. In certain embodiments, theethylene/α-olefin interpolymer has a melt index in the range of about 1to about 1500 g/10 minutes, about 2 to about 1000 g/10 minutes or about5 to about 500 g/10 minutes measured according to ASTM D-1238, Condition190° C./2.16 kg. In certain embodiments, the ethylene/α-olefininterpolymer has a melt index in the range of about 5 to about 50 g/10minutes or about 10 to about 30 g/10 minutes measured according to ASTMD-1238, Condition 190° C./2.16 kg.

In one embodiment, the overall density of the ethylene/α-olefininterpolymer is from about 0.85 to 0.88 g/cc or from about 0.86 to 0.875g/cc.

In certain embodiments, the range of the ethylene/α-olefin interpolymerin the compositions provided herein is from about 10% to about 50% byweight of the total composition. In certain embodiments, theethylene/α-olefin interpolymer is in the range from about 15% to about30% by weight of the total composition.

In certain embodiments, the amount of tackifier in the adhesivecompositions is in the range from about 5% to about 70% by weight of thetotal composition. In certain embodiments, the tackifier is present inthe range from about 20% to about 70% by weight of the totalcomposition.

In certain embodiments, the tackifier is at least one of a natural andmodified resin; a glycerol or pentaerythritol ester of natural ormodified rosin; a copolymer or terpolymer of natured terpene; apolyterpene resin or a hydrogenated polyterpene resin; a phenolicmodified terpene resin or a hydrogenated derivative thereof; analiphatic or cycloaliphatic hydrocarbon resin or a hydrogenatedderivative thereof; an aromatic hydrocarbon resin or a hydrogenatedderivative thereof; an aromatic modified aliphatic or cycloaliphatichydrocarbon resin or a hydrogenated derivative thereof; or a combinationthereof. When the tackifier is an aliphatic hydrocarbon resin, it canhave at least five carbon atoms. In certain embodiments, the tackifierhas a R&B softening point equal to or greater than 80° C.

In certain embodiments, the adhesive compositions provided hereincomprise an additive selected from the group consisting of plasticizers,oils, waxes, antioxidants, UV stabilizers, colorants or pigments,fillers, flow aids, coupling agents, crosslinking agents, surfactants,solvents, and combinations thereof. In certain embodiments, the additiveis plasticizer, such as a mineral oil, liquid polybutene or acombination thereof.

In certain embodiments, the compositions, further comprise a wax, suchas a petroleum wax, a low molecular weight polyethylene orpolypropylene, a synthetic wax, a polyolefin wax, a beeswax, a vegetablewax, a soy wax, a palm wax, a candle wax or an ethylene/α-olefininterpolymer having a melting point of greater than 25° C. In certainembodiments, the wax is a low molecular weight polyethylene orpolypropylene having a number average molecular weight of about 400 toabout 6,000 g/mole. The wax can be present in the range from about 10%to about 50% or 20% to about 40% by weight of the total composition.

In certain embodiments, the composition further comprises anantioxidant. The antioxidant can be present in the range from greaterthan 0% to about 1% or about 0.05% to about 0.75% by weight of the totalcomposition.

In certain embodiments, the composition further comprises a filler. Thefiller can be in the amount up to 80% by weight of the totalcomposition. The filler can be selected from sand, talc, dolomite,calcium carbonate, clay, silica, mica, wollastonite, feldspar, aluminumsilicate, alumina, hydrated alumina, glass bead, glass microsphere,ceramic microsphere, thermoplastic microsphere, barite, wood flour, or acombination thereof.

In certain embodiments, the compositions provided herein have a shearadhesion failure temperature of at least 32° C., 43° C., 54° C. or 66°C.

In certain embodiments, the composition has a 180° peel adhesion to apolyester substrate of at least about 100 N/dm. In certain embodiments,the composition has a 180° peel adhesion to a stainless substrategreater than 0.1 lbs, greater than 1.5 lbs or greater than 3 lbs. Incertain embodiments, the composition has a 180° peel adhesion to apolypropylene substrate greater than 0.1 lbs, greater than 1.5 lbs orgreater than 3 lbs.

In certain embodiments, the composition has a Brookfield viscosity fromabout 500 and 50,000 cp at 177° C. In certain embodiments, thecomposition has the G′(25° C.) from about 1×10³ to about 1×10⁶ Pa, fromabout 2×10³ to about 5×10⁵ Pa, or from about 1×10⁴ to about 5×10⁵ Pa.

In certain embodiments, the ratio of G′(25° C.) to G′(75° C.) in thecompositions provided herein is from about 1:1 to about 110:1, fromabout 1:1 to about 75:1, from about 1:1 to about 25:1, from about 1:1 toabout 20:1, from about 1:1 to about 15:1, from about 1:1 to about 10:1,from about 1:1 to about 9:1, from about 1:1 to about 8:1, from about 1:1to about 7:1, from about 1:1 to about 6:1, from about 1:1 to about 5:1,or from about 1:1 to about 4:1.

In certain embodiments, the loop tack of the adhesive compositionsprovided herein is greater than about 0.5 lb, greater than about 1 lb,or greater than about 2 lb.

In certain embodiments, the compositions have a SAFT of the hot meltadhesive composition that is greater than about 130° F., greater thanabout 140° F., or greater than about 150° F. Certain of the compositionherein have a SAFT greater than about 180° F., greater than about 190°F., or greater than about 200° F. In certain embodiments, the SAFT ofthe pressure sensitive adhesive composition is greater than 54° C. Incertain embodiments, the SAFT of the pressure sensitive adhesivecompositions provided herein is greater than or equal to 90° F., greaterthan or equal to 110° F., greater than or equal to 130° F. or greaterthan or equal to 150° F. In certain embodiments, the fiber tear of thepressure sensitive adhesive composition is 100% at a temperature fromabout 25 to about 60° C.

In certain embodiments, the thermoplastic marking compositions providedherein further comprise a filler and a pigment. The filler can compriseglass microspheres or glass beads. In certain embodiments, thethermoplastic marking composition is in the form of a hot melt extrusionroad marking, hot melt spray road marking, hot melt hand applied roadmarking, colored hot melt marked bicycle lane, simulation or trainingroad marking, preformed extruded traffic symbol or tape, flexible andsoft sports/playground surface marking, safety marking on a ship, or areflective traffic safety coating.

In certain embodiments, an article comprising a substrate coated withthe composition described herein is provided. The article is selectedfrom a tape, a label, a decal, a case, a carton, a tray, a medicaldevice, a bandage and a hygiene article.

In another aspect, the invention relates to methods of making acomposition, comprising: blending the ethylene/α-olefin interpolymerwith a tackifier. The ethylene/α-olefin interpolymer is described aboveand elsewhere herein. In certain embodiments, the method furthercomprises blending an additive selected from the group consisting ofplasticizers, oils, waxes, antioxidants, UV stabilizers, colorants orpigments, fillers, flow aids, coupling agents, crosslinking agents,surfactants, solvents, and combinations thereof. In certain embodiments,the additive is a plasticizer or an oil. In certain embodiments, theadditive is a wax. In certain embodiments, the additive is anantioxidant. In certain embodiments, the additive is a pigment. Incertain embodiments, the additive is a filler. In certain embodiments,the filler comprises glass beads or glass microspheres.

Additional aspects of the invention and characteristics and propertiesof various embodiments of the invention become apparent with thefollowing description.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the melting point/density relationship for the inventivepolymers (represented by diamonds) as compared to traditional randomcopolymers (represented by circles) and Ziegler-Natta copolymers(represented by triangles).

FIG. 2 shows plots of delta DSC-CRYSTAF as a function of DSC MeltEnthalpy for various polymers. The diamonds represent randomethylene/octene copolymers; the squares represent polymer examples 1-4;the triangles represent polymer examples 5-9; and the circles representpolymer examples 10-19. The “X” symbols represent polymer examplesA*-F*.

FIG. 3 shows the effect of density on elastic recovery for unorientedfilms made from the inventive interpolymers (represented by the squaresand circles) and traditional copolymers (represented by the triangleswhich are various Dow AFFINITY® polymers). The squares representinventive ethylene/butene copolymers; and the circles representinventive ethylene/octene copolymers.

FIG. 4 is a plot of octene content of TREF fractionatedethylene/1-octene copolymer fractions versus TREF elution temperature ofthe fraction for the polymer of Example 5 (represented by the circles)and Comparative Example E* and F* (represented by the “X” symbols). Thediamonds represent traditional random ethylene/octene copolymers.

FIG. 5 is a plot of octene content of TREF fractionatedethylene/1-octene copolymer fractions versus TREF elution temperature ofthe fraction for the polymer of Example 5 (curve 1) and for ComparativeExample F* (curve 2). The squares represent Example F*; and thetriangles represent Example 5.

FIG. 6 is a graph of the log of storage modulus as a function oftemperature for comparative ethylene/1-octene copolymer (curve 2) andpropylene/ethylene-copolymer (curve 3) and for two ethylene/1-octeneblock copolymers of the invention made with differing quantities ofchain shuttling agent (curves 1).

FIG. 7 shows a plot of TMA (1 mm) versus flex modulus for some inventivepolymers (represented by the diamonds), as compared to some knownpolymers. The triangles represent various Dow VERSIFY® polymers; thecircles represent various random ethylene/styrene copolymers; and thesquares represent various Dow AFFINITY® polymers.

FIG. 8 shows plots of Storage Modulus (G′) versus temperature forExamples 32 (represented by the circles) and 33 (represented by the opensquares) as compared to Comparative Examples L (represented by the soliddiamonds) and M (represented by the “X” symbols).

FIG. 9 shows plots of Storage Modulus (G′) versus temperature forExamples 34 (represented by the open circles), 35 (represented by theopen squares) and 36 (represented by the open diamonds), as compared toComparative Examples N (represented by the solid circles), P(represented by the solid squares) and Q (represented by the soliddiamonds).

FIG. 10 shows a DSC second heating curve for Polymer Example 30.

FIG. 11 shows a DSC second heating curve for Polymer Example 31c.

FIG. 12 shows a DSC second heating curve for Polymer Example 31d.

DETAILED DESCRIPTION OF THE INVENTION General Definitions

“Polymer” means a polymeric compound prepared by polymerizing monomers,whether of the same or a different type. The generic term “polymer”embraces the terms “homopolymer,” “copolymer,” “terpolymer” as well as“interpolymer.”

“Interpolymer” means a polymer prepared by the polymerization of atleast two different types of monomers. The generic term “interpolymer”includes the term “copolymer” (which is usually employed to refer to apolymer prepared from two different monomers) as well as the term“terpolymer” (which is usually employed to refer to a polymer preparedfrom three different types of monomers). It also encompasses polymersmade by polymerizing four or more types of monomers.

The term “ethylene/α-olefin interpolymer” generally refers to polymerscomprising ethylene and an α-olefin having 3 or more carbon atoms.Preferably, ethylene comprises the majority mole fraction of the wholepolymer, i.e., ethylene comprises at least about 50 mole percent of thewhole polymer. More preferably ethylene comprises at least about 60 molepercent, at least about 70 mole percent, or at least about 80 molepercent, with the substantial remainder of the whole polymer comprisingat least one other comonomer that is preferably an α-olefin having 3 ormore carbon atoms. For many ethylene/octene copolymers, the preferredcomposition comprises an ethylene content greater than about 80 molepercent of the whole polymer and an octene content of from about 10 toabout 15, preferably from about 15 to about 20 mole percent of the wholepolymer. In some embodiments, the ethylene/α-olefin interpolymers do notinclude those produced in low yields or in a minor amount or as aby-product of a chemical process. While the ethylene/α-olefininterpolymers can be blended with one or more polymers, the as-producedethylene/α-olefin interpolymers are substantially pure and oftencomprise a major component of the reaction product of a polymerizationprocess.

The ethylene/α-olefin interpolymers comprise ethylene and one or morecopolymerizable α-olefin comonomers in polymerized form, characterizedby multiple blocks or segments of two or more polymerized monomer unitsdiffering in chemical or physical properties. That is, theethylene/α-olefin interpolymers are block interpolymers, preferablymulti-block interpolymers or copolymers. The terms “interpolymer” andcopolymer” are used interchangeably herein. In some embodiments, themulti-block copolymer can be represented by the following formula:(AB)_(n)where n is at least 1, preferably an integer greater than 1, such as 2,3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, or higher, “A”represents a hard block or segment and “B” represents a soft block orsegment. Preferably, As and Bs are linked in a substantially linearfashion, as opposed to a substantially branched or substantiallystar-shaped fashion. In other embodiments, A blocks and B blocks arerandomly distributed along the polymer chain. In other words, the blockcopolymers usually do not have a structure as follows.AAA-AA-BBB-BBIn still other embodiments, the block copolymers do not usually have athird type of block, which comprises different comonomer(s). In yetother embodiments, each of block A and block B has monomers orcomonomers substantially randomly distributed within the block. In otherwords, neither block A nor block B comprises two or more sub-segments(or sub-blocks) of distinct composition, such as a tip segment, whichhas a substantially different composition than the rest of the block.

The multi-block polymers typically comprise various amounts of “hard”and “soft” segments. “Hard” segments refer to blocks of polymerizedunits in which ethylene is present in an amount greater than about 95weight percent, and preferably greater than about 98 weight percentbased on the weight of the polymer. In other words, the comonomercontent (content of monomers other than ethylene) in the hard segmentsis less than about 5 weight percent, and preferably less than about 2weight percent based on the weight of the polymer. In some embodiments,the hard segments comprises all or substantially all ethylene. “Soft”segments, on the other hand, refer to blocks of polymerized units inwhich the comonomer content (content of monomers other than ethylene) isgreater than about 5 weight percent, preferably greater than about 8weight percent, greater than about 10 weight percent, or greater thanabout 15 weight percent based on the weight of the polymer. In someembodiments, the comonomer content in the soft segments can be greaterthan about 20 weight percent, greater than about 25 weight percent,greater than about 30 weight percent, greater than about 35 weightpercent, greater than about 40 weight percent, greater than about 45weight percent, greater than about 50 weight percent, or greater thanabout 60 weight percent.

The soft segments can often be present in a block interpolymer fromabout 1 weight percent to about 99 weight percent of the total weight ofthe block interpolymer, preferably from about 5 weight percent to about95 weight percent, from about 10 weight percent to about 90 weightpercent, from about 15 weight percent to about 85 weight percent, fromabout 20 weight percent to about 80 weight percent, from about 25 weightpercent to about 75 weight percent, from about 30 weight percent toabout 70 weight percent, from about 35 weight percent to about 65 weightpercent, from about 40 weight percent to about 60 weight percent, orfrom about 45 weight percent to about 55 weight percent of the totalweight of the block interpolymer. Conversely, the hard segments can bepresent in similar ranges. The soft segment weight percentage and thehard segment weight percentage can be calculated based on data obtainedfrom DSC or NMR. Such methods and calculations are disclosed in aconcurrently filed U.S. patent application Ser. No. 11/376,835, entitled“Ethylene/α-Olefin Block Interpolymers”, filed on Mar. 15, 2006, in thename of Colin L. P. Shan, Lonnie Hazlitt, et. al. and assigned to DowGlobal Technologies Inc., the disclose of which is incorporated byreference herein in its entirety.

The term “crystalline” if employed, refers to a polymer that possesses afirst order transition or crystalline melting point (Tm) as determinedby differential scanning calorimetry (DSC) or equivalent technique. Theterm may be used interchangeably with the term “semicrystalline”. Theterm “amorphous” refers to a polymer lacking a crystalline melting pointas determined by differential scanning calorimetry (DSC) or equivalenttechnique.

The term “multi-block copolymer” or “segmented copolymer” refers to apolymer comprising two or more chemically distinct regions or segments(referred to as “blocks”) preferably joined in a linear manner, that is,a polymer comprising chemically differentiated units which are joinedend-to-end with respect to polymerized ethylenic functionality, ratherthan in pendent or grafted fashion. In a preferred embodiment, theblocks differ in the amount or type of comonomer incorporated therein,the density, the amount of crystallinity, the crystallite sizeattributable to a polymer of such composition, the type or degree oftacticity (isotactic or syndiotactic), regio-regularity orregio-irregularity, the amount of branching, including long chainbranching or hyper-branching, the homogeneity, or any other chemical orphysical property. The multi-block copolymers are characterized byunique distributions of both polydispersity index (PDI or Mw/Mn), blocklength distribution, and/or block number distribution due to the uniqueprocess of making the copolymers. More specifically, when produced in acontinuous process, the polymers desirably possess PDI from 1.7 to 2.9,preferably from 1.8 to 2.5, more preferably from 1.8 to 2.2, and mostpreferably from 1.8 to 2.1. When produced in a batch or semi-batchprocess, the polymers possess PDI from 1.0 to 2.9, preferably from 1.3to 2.5, more preferably from 1.4 to 2.0, and most preferably from 1.4 to1.8.

In the following description, all numbers disclosed herein areapproximate values, regardless whether the word “about” or “approximate”is used in connection therewith. They may vary by 1 percent, 2 percent,5 percent, or, sometimes, 10 to 20 percent. Whenever a numerical rangewith a lower limit, R^(L) and an upper limit, R^(U), is disclosed, anynumber falling within the range is specifically disclosed. Inparticular, the following numbers within the range are specificallydisclosed: R=R^(L)+k*(R^(U)−R^(L)), wherein k is a variable ranging from1 percent to 100 percent with a 1 percent increment, i.e., k is 1percent, 2 percent, 3 percent, 4 percent, 5 percent, . . . , 50 percent,51 percent, 52 percent, . . . , 95 percent, 96 percent, 97 percent, 98percent, 99 percent, or 100 percent. Moreover, any numerical rangedefined by two R numbers as defined in the above is also specificallydisclosed.

Embodiments of the invention provide compositions that comprise anethylene/α-olefin interpolymer and a tackifier resin. The compositionspossess unique properties that are suitable for a variety ofapplications, particularly where a certain level of adhesion isrequired. Some non-limiting examples of suitable applications includehot melt adhesives, pressure sensitive adhesives, thermoplastic markingcompositions, and the like. Preferably, the ethylene/α-olefininterpolymers are a multi-block copolymer comprising at least one softblock and at least one hard block.

In some embodiments, the composition has a shear adhesion failuretemperature (SAFT) of at least 90° F. (32° C.), at least 110° F. (43°C.), at least 130° F. (54° C.), or at least 150° F. (66° C.). The SAFTis a measure of the upper service temperature of the composition and canbe determined by the method described in ASTM D4498, which isincorporated herein by reference. In further embodiments, thecomposition has a 180° peel adhesion of at least about 100 N/dm. The180° peel adhesion of the composition can be measured by bondingstainless steel to Mylar using the method described in the PressureSensitive Tape Council (PSTC)-1, which is incorporated herein byreference.

In other embodiments, the adhesive compositions have a low meltviscosity so that it is easy to process the composition withoutresorting to the inclusion of solvents or excess plasticizer into thecompositions. The melt viscosities of the compositions can be measuredby a Brookfield viscometer using appropriate spindles as by ASTM D3236at about 350° F. (177° C.), which is incorporated herein by reference.In some embodiments, the composition has a melt viscosity of less than20,000 cps at about 177° C., or less than about 10,000 at 177° C., orless than about 5,000 at 177° C. measured according to ASTM D3236.

Ethylene/α-Olefin Interpolymers

The ethylene/α-olefin interpolymers used in embodiments of the invention(also referred to as “inventive interpolymer” or “inventive polymer”)comprise ethylene and one or more copolymerizable α-olefin comonomers inpolymerized form, characterized by multiple blocks or segments of two ormore polymerized monomer units differing in chemical or physicalproperties (block interpolymer), preferably a multi-block copolymer. Theethylene/α-olefin interpolymers are characterized by one or more of theaspects described as follows.

In one aspect, the ethylene/α-olefin interpolymers used in embodimentsof the invention have a M_(w)/M_(n) from about 1.7 to about 3.5 and atleast one melting point, T_(m), in degrees Celsius and density, d, ingrams/cubic centimeter, wherein the numerical values of the variablescorrespond to the relationship:T _(m)>−2002.9+4538.5(d)−2422.2(d)², and preferablyT _(m)≧−6288.1+13141(d)−6720.3(d)², and more preferablyT _(m)≧858.91−1825.3(d)+1112.8(d)².

Such melting point/density relationship is illustrated in FIG. 1. Unlikethe traditional random copolymers of ethylene/α-olefins whose meltingpoints decrease with decreasing densities, the inventive interpolymers(represented by diamonds) exhibit melting points substantiallyindependent of the density, particularly when density is between about0.87 g/cc to about 0.95 g/cc. For example, the melting point of suchpolymers are in the range of about 110° C. to about 130° C. when densityranges from 0.875 g/cc to about 0.945 g/cc. In some embodiments, themelting point of such polymers are in the range of about 115° C. toabout 125° C. when density ranges from 0.875 g/cc to about 0.945 g/cc.

In another aspect, the ethylene/α-olefin interpolymers comprise, inpolymerized form, ethylene and one or more α-olefins and arecharacterized by a ΔT, in degree Celsius, defined as the temperature forthe tallest Differential Scanning Calorimetry (“DSC”) peak minus thetemperature for the tallest Crystallization Analysis Fractionation(“CRYSTAF”) peak and a heat of fusion in J/g, ΔH, and ΔT and ΔH satisfythe following relationships:ΔT>−0.1299(ΔH)+62.81, and preferablyΔT≧−0.1299(ΔH)+64.38, and more preferablyΔT≧−0.1299(ΔH)+65.95,for ΔH up to 130 J/g. Moreover, ΔT is equal to or greater than 48° C.for ΔH greater than 130 J/g. The CRYSTAF peak is determined using atleast 5 percent of the cumulative polymer (that is, the peak mustrepresent at least 5 percent of the cumulative polymer), and if lessthan 5 percent of the polymer has an identifiable CRYSTAF peak, then theCRYSTAF temperature is 30° C., and ΔH is the numerical value of the heatof fusion in J/g. More preferably, the highest CRYSTAF peak contains atleast 10 percent of the cumulative polymer. FIG. 2 shows plotted datafor inventive polymers as well as comparative examples. Integrated peakareas and peak temperatures are calculated by the computerized drawingprogram supplied by the instrument maker. The diagonal line shown forthe random ethylene octene comparative polymers corresponds to theequation ΔT=−0.1299 (ΔH)+62.81.

In yet another aspect, the ethylene/α-olefin interpolymers have amolecular fraction which elutes between 40° C. and 130° C. whenfractionated using Temperature Rising Elution Fractionation (“TREF”),characterized in that said fraction has a molar comonomer contenthigher, preferably at least 5 percent higher, more preferably at least10 percent higher, than that of a comparable random ethyleneinterpolymer fraction eluting between the same temperatures, wherein thecomparable random ethylene interpolymer contains the same comonomer(s),and has a melt index, density, and molar comonomer content (based on thewhole polymer) within 10 percent of that of the block interpolymer.Preferably, the Mw/Mn of the comparable interpolymer is also within 10percent of that of the block interpolymer and/or the comparableinterpolymer has a total comonomer content within 10 weight percent ofthat of the block interpolymer.

In still another aspect, the ethylene/α-olefin interpolymers arecharacterized by an elastic recovery, Re, in percent at 300 percentstrain and 1 cycle measured on a compression-molded film of anethylene/α-olefin interpolymer, and has a density, d, in grams/cubiccentimeter, wherein the numerical values of Re and d satisfy thefollowing relationship when ethylene/α-olefin interpolymer issubstantially free of a cross-linked phase:Re>1481−1629(d); and preferablyRe≧1491−1629(d); and more preferablyRe≧1501−1629(d); and even more preferablyRe≧1511−1629(d).

FIG. 3 shows the effect of density on elastic recovery for unorientedfilms made from certain inventive interpolymers and traditional randomcopolymers. For the same density, the inventive interpolymers havesubstantially higher elastic recoveries.

In some embodiments, the ethylene/α-olefin interpolymers have a tensilestrength above 10 MPa, preferably a tensile strength≧11 MPa, morepreferably a tensile strength≧13 MPa and/or an elongation at break of atleast 600 percent, more preferably at least 700 percent, highlypreferably at least 800 percent, and most highly preferably at least 900percent at a crosshead separation rate of 11 cm/minute.

In other embodiments, the ethylene/α-olefin interpolymers have (1) astorage modulus ratio, G′(25° C.)/G′(100° C.), of from 1 to 50,preferably from 1 to 20, more preferably from 1 to 10; and/or (2) a 70°C. compression set of less than 80 percent, preferably less than 70percent, especially less than 60 percent, less than 50 percent, or lessthan 40 percent, down to a compression set of 0 percent.

In still other embodiments, the ethylene/α-olefin interpolymers have a70° C. compression set of less than 80 percent, less than 70 percent,less than 60 percent, or less than 50 percent. Preferably, the 70° C.compression set of the interpolymers is less than 40 percent, less than30 percent, less than 20 percent, and may go down to about 0 percent.

In some embodiments, the ethylene/α-olefin interpolymers have a heat offusion of less than 85 J/g and/or a pellet blocking strength of equal toor less than 100 pounds/foot² (4800 Pa), preferably equal to or lessthan 50 lbs/ft² (2400 Pa), especially equal to or less than 5 lbs/ft²(240 Pa), and as low as 0 lbs/ft² (0 Pa).

In other embodiments, the ethylene/α-olefin interpolymers comprise, inpolymerized form, at least 50 mole percent ethylene and have a 70° C.compression set of less than 80 percent, preferably less than 70 percentor less than 60 percent, most preferably less than 40 to 50 percent anddown to close zero percent.

In some embodiments, the multi-block copolymers possess a PDI fitting aSchultz-Flory distribution rather than a Poisson distribution. Thecopolymers are further characterized as having both a polydisperse blockdistribution and a polydisperse distribution of block sizes andpossessing a most probable distribution of block lengths. Preferredmulti-block copolymers are those containing 4 or more blocks or segmentsincluding terminal blocks. More preferably, the copolymers include atleast 5, 10 or 20 blocks or segments including terminal blocks.

Comonomer content may be measured using any suitable technique, withtechniques based on nuclear magnetic resonance (“NMR”) spectroscopypreferred. Moreover, for polymers or blends of polymers havingrelatively broad TREF curves, the polymer desirably is firstfractionated using TREF into fractions each having an eluted temperaturerange of 10° C. or less. That is, each eluted fraction has a collectiontemperature window of 10° C. or less. Using this technique, said blockinterpolymers have at least one such fraction having a higher molarcomonomer content than a corresponding fraction of the comparableinterpolymer.

In another aspect, the inventive polymer is an olefin interpolymer,preferably comprising ethylene and one or more copolymerizablecomonomers in polymerized form, characterized by multiple blocks (i.e.,at least two blocks) or segments of two or more polymerized monomerunits differing in chemical or physical properties (blockedinterpolymer), most preferably a multi-block copolymer, said blockinterpolymer having a peak (but not just a molecular fraction) whichelutes between 40° C. and 130° C. (but without collecting and/orisolating individual fractions), characterized in that said peak, has acomonomer content estimated by infra-red spectroscopy when expandedusing a full width/half maximum (FWHM) area calculation, has an averagemolar comonomer content higher, preferably at least 5 percent higher,more preferably at least 10 percent higher, than that of a comparablerandom ethylene interpolymer peak at the same elution temperature andexpanded using a full width/half maximum (FWHM) area calculation,wherein said comparable random ethylene interpolymer has the samecomonomer(s) and has a melt index, density, and molar comonomer content(based on the whole polymer) within 10 percent of that of the blockedinterpolymer. Preferably, the Mw/Mn of the comparable interpolymer isalso within 10 percent of that of the blocked interpolymer and/or thecomparable interpolymer has a total comonomer content within 10 weightpercent of that of the blocked interpolymer. The full width/half maximum(FWHM) calculation is based on the ratio of methyl to methylene responsearea [CH₃/CH₂] from the ATREF infra-red detector, wherein the tallest(highest) peak is identified from the base line, and then the FWHM areais determined. For a distribution measured using an ATREF peak, the FWHMarea is defined as the area under the curve between T₁ and T₂, where T₁and T₂ are points determined, to the left and right of the ATREF peak,by dividing the peak height by two, and then drawing a line horizontalto the base line, that intersects the left and right portions of theATREF curve. A calibration curve for comonomer content is made usingrandom ethylene/α-olefin copolymers, plotting comonomer content from NMRversus FWHM area ratio of the TREF peak. For this infra-red method, thecalibration curve is generated for the same comonomer type of interest.The comonomer content of TREF peak of the inventive polymer can bedetermined by referencing this calibration curve using its FWHMmethyl:methylene area ratio [CH₃/CH₂] of the TREF peak.

Comonomer content may be measured using any suitable technique, withtechniques based on nuclear magnetic resonance (NMR) spectroscopypreferred. Using this technique, said blocked interpolymers have highermolar comonomer content than a corresponding comparable interpolymer.

Preferably, for interpolymers of ethylene and 1-octene, the blockinterpolymer has a comonomer content of the TREF fraction elutingbetween 40 and 130° C. greater than or equal to the quantity (−0.2013)T+20.07, more preferably greater than or equal to the quantity (−0.2013)T+21.07, where T is the numerical value of the peak elution temperatureof the TREF fraction being compared, measured in ° C.

FIG. 4 graphically depicts an embodiment of the block interpolymers ofethylene and 1-octene where a plot of the comonomer content versus TREFelution temperature for several comparable ethylene/1-octeneinterpolymers (random copolymers) are fit to a line representing(−0.2013) T+20.07 (solid line). The line for the equation (−0.2013)T+21.07 is depicted by a dotted line. Also depicted are the comonomercontents for fractions of several block ethylene/1-octene interpolymersof the invention (multi-block copolymers). All of the block interpolymerfractions have significantly higher 1-octene content than either line atequivalent elution temperatures. This result is characteristic of theinventive interpolymer and is believed to be due to the presence ofdifferentiated blocks within the polymer chains, having both crystallineand amorphous nature.

FIG. 5 graphically displays the TREF curve and comonomer contents ofpolymer fractions for Example 5 and Comparative Example F* to bediscussed below. The peak eluting from 40 to 130° C., preferably from60° C. to 95° C. for both polymers is fractionated into three parts,each part eluting over a temperature range of less than 10° C. Actualdata for Example 5 is represented by triangles. The skilled artisan canappreciate that an appropriate calibration curve may be constructed forinterpolymers containing different comonomers and a line used as acomparison fitted to the TREF values obtained from comparativeinterpolymers of the same monomers, preferably random copolymers madeusing a metallocene or other homogeneous catalyst composition. Inventiveinterpolymers are characterized by a molar comonomer content greaterthan the value determined from the calibration curve at the same TREFelution temperature, preferably at least 5 percent greater, morepreferably at least 10 percent greater.

In addition to the above aspects and properties described herein, theinventive polymers can be characterized by one or more additionalcharacteristics. In one aspect, the inventive polymer is an olefininterpolymer, preferably comprising ethylene and one or morecopolymerizable comonomers in polymerized form, characterized bymultiple blocks or segments of two or more polymerized monomer unitsdiffering in chemical or physical properties (blocked interpolymer),most preferably a multi-block copolymer, said block interpolymer havinga molecular fraction which elutes between 40° C. and 130° C., whenfractionated using TREF increments, characterized in that said fractionhas a molar comonomer content higher, preferably at least 5 percenthigher, more preferably at least 10, 15, 20 or 25 percent higher, thanthat of a comparable random ethylene interpolymer fraction elutingbetween the same temperatures, wherein said comparable random ethyleneinterpolymer comprises the same comonomer(s), preferably it is the samecomonomer(s), and a melt index, density, and molar comonomer content(based on the whole polymer) within 10 percent of that of the blockedinterpolymer. Preferably, the Mw/Mn of the comparable interpolymer isalso within 10 percent of that of the blocked interpolymer and/or thecomparable interpolymer has a total comonomer content within 10 weightpercent of that of the blocked interpolymer.

Preferably, the above interpolymers are interpolymers of ethylene and atleast one α-olefin, especially those interpolymers having a wholepolymer density from about 0.855 to about 0.935 g/cm³, and moreespecially for polymers having more than about 1 mole percent comonomer,the blocked interpolymer has a comonomer content of the TREF fractioneluting between 40 and 130° C. greater than or equal to the quantity(−0.1356) T+13.89, more preferably greater than or equal to the quantity(−0.1356) T+14.93, and most preferably greater than or equal to thequantity (−0.2013) T+21.07, where T is the numerical value of the peakATREF elution temperature of the TREF fraction being compared, measuredin ° C.

Preferably, for the above interpolymers of ethylene and at least onealpha-olefin especially those interpolymers having a whole polymerdensity from about 0.855 to about 0.935 g/cm³, and more especially forpolymers having more than about 1 mole percent comonomer, the blockedinterpolymer has a comonomer content of the TREF fraction elutingbetween 40 and 130° C. greater than or equal to the quantity (−0.2013)T+20.07, more preferably greater than or equal to the quantity (−0.2013)T+21.07, where T is the numerical value of the peak elution temperatureof the TREF fraction being compared, measured in ° C.

In still another aspect, the inventive polymer is an olefininterpolymer, preferably comprising ethylene and one or morecopolymerizable comonomers in polymerized form, characterized bymultiple blocks or segments of two or more polymerized monomer unitsdiffering in chemical or physical properties (blocked interpolymer),most preferably a multi-block copolymer, said block interpolymer havinga molecular fraction which elutes between 40° C. and 130° C., whenfractionated using TREF increments, characterized in that every fractionhaving a comonomer content of at least about 6 mole percent, has amelting point greater than about 100° C. For those fractions having acomonomer content from about 3 mole percent to about 6 mole percent,every fraction has a DSC melting point of about 110° C. or higher. Morepreferably, said polymer fractions, having at least 1 mol percentcomonomer, has a DSC melting point that corresponds to the equation:Tm≧(−5.5926)(mol percent comonomer in the fraction)+135.90.

In yet another aspect, the inventive polymer is an olefin interpolymer,preferably comprising ethylene and one or more copolymerizablecomonomers in polymerized form, characterized by multiple blocks orsegments of two or more polymerized monomer units differing in chemicalor physical properties (blocked interpolymer), most preferably amulti-block copolymer, said block interpolymer having a molecularfraction which elutes between 40° C. and 130° C., when fractionatedusing TREF increments, characterized in that every fraction that has anATREF elution temperature greater than or equal to about 76° C., has amelt enthalpy (heat of fusion) as measured by DSC, corresponding to theequation:Heat of fusion (J/gm)≦(3.1718)(ATREF elution temperature inCelsius)−136.58,

The inventive block interpolymers have a molecular fraction which elutesbetween 40° C. and 130° C., when fractionated using TREF increments,characterized in that every fraction that has an ATREF elutiontemperature between 40° C. and less than about 76° C., has a meltenthalpy (heat of fusion) as measured by DSC, corresponding to theequation:Heat of fusion (J/gm)≦(1.1312)(ATREF elution temperature inCelsius)+22.97.ATREF Peak Comonomer Composition Measurement by Infra-Red Detector

The comonomer composition of the TREF peak can be measured using an IR4infra-red detector available from Polymer Char, Valencia, Spain(http://www.polymerchar.com/).

The “composition mode” of the detector is equipped with a measurementsensor (CH₂) and composition sensor (CH₃) that are fixed narrow bandinfra-red filters in the region of 2800-3000 cm⁻¹. The measurementsensor detects the methylene (CH₂) carbons on the polymer (whichdirectly relates to the polymer concentration in solution) while thecomposition sensor detects the methyl (CH₃) groups of the polymer. Themathematical ratio of the composition signal (CH₃) divided by themeasurement signal (CH₂) is sensitive to the comonomer content of themeasured polymer in solution and its response is calibrated with knownethylene alpha-olefin copolymer standards.

The detector when used with an ATREF instrument provides both aconcentration (CH₂) and composition (CH₃) signal response of the elutedpolymer during the TREF process. A polymer specific calibration can becreated by measuring the area ratio of the CH₃ to CH₂ for polymers withknown comonomer content (preferably measured by NMR). The comonomercontent of an ATREF peak of a polymer can be estimated by applying a thereference calibration of the ratio of the areas for the individual CH₃and CH₂ response (i.e. area ratio CH₃/CH₂ versus comonomer content).

The area of the peaks can be calculated using a full width/half maximum(FWHM) calculation after applying the appropriate baselines to integratethe individual signal responses from the TREF chromatogram. The fullwidth/half maximum calculation is based on the ratio of methyl tomethylene response area [CH₃/CH₂] from the ATREF infra-red detector,wherein the tallest (highest) peak is identified from the base line, andthen the FWHM area is determined. For a distribution measured using anATREF peak, the FWHM area is defined as the area under the curve betweenT1 and T2, where T1 and T2 are points determined, to the left and rightof the ATREF peak, by dividing the peak height by two, and then drawinga line horizontal to the base line, that intersects the left and rightportions of the ATREF curve.

The application of infra-red spectroscopy to measure the comonomercontent of polymers in this ATREF-infra-red method is, in principle,similar to that of GPC/FTIR systems as described in the followingreferences: Markovich, Ronald P.; Hazlitt, Lonnie G.; Smith, Linley;“Development of gel-permeation chromatography-Fourier transform infraredspectroscopy for characterization of ethylene-based polyolefincopolymers”, Polymeric Materials Science and Engineering (1991), 65,98-100.; and Deslauriers, P. J.; Rohlfing, D. C.; Shieh, E. T.;“Quantifying short chain branching microstructures in ethylene-1-olefincopolymers using size exclusion chromatography and Fourier transforminfrared spectroscopy (SEC-FTIR)”, Polymer (2002), 43, 59-170, both ofwhich are incorporated by reference herein in their entirety.

In other embodiments, the inventive ethylene/α-olefin interpolymer ischaracterized by an average block index, ABI, which is greater than zeroand up to about 1.0 and a molecular weight distribution, M_(w)/M_(n),greater than about 1.3. The average block index, ABI, is the weightaverage of the block index (“BI”) for each of the polymer fractionsobtained in preparative TREF from 20° C. and 110° C., with an incrementof 5° C.:ABI=Σ(w _(i) BI _(i))where BI_(i) is the block index for the ith fraction of the inventiveethylene/α-olefin interpolymer obtained in preparative TREF, and w_(i)is the weight percentage of the ith fraction.

For each polymer fraction, BI is defined by one of the two followingequations (both of which give the same BI value):

${BI} = {{\frac{{1/T_{X}} - {1/T_{X\; O}}}{{1/T_{A}} - {1/T_{AB}}}\mspace{14mu}{or}\mspace{14mu}{BI}} = {- \frac{{LnP}_{X} - {LnP}_{XO}}{{LnP}_{A} - {LnP}_{AB}}}}$where T_(x) is the preparative ATREF elution temperature for the ithfraction (preferably expressed in Kelvin), P_(x) is the ethylene molefraction for the ith fraction, which can be measured by NMR or IR asdescribed above. P_(AB) is the ethylene mole fraction of the wholeethylene/α-olefin interpolymer (before fractionation), which also can bemeasured by NMR or IR. T_(A) and P_(A) are the ATREF elution temperatureand the ethylene mole fraction for pure “hard segments” (which refer tothe crystalline segments of the interpolymer). As a first orderapproximation, the T_(A) and P_(A) values are set to those for highdensity polyethylene homopolymer, if the actual values for the “hardsegments” are not available. For calculations performed herein, T_(A) is372° K., P_(A) is 1.

T_(AB) is the ATREF temperature for a random copolymer of the samecomposition and having an ethylene mole fraction of P_(AB). T_(AB) canbe calculated from the following equation:Ln P _(AB) =α/T _(AB)+β

where α and β are two constants which can be determined by calibrationusing a number of known random ethylene copolymers. It should be notedthat α and β may vary from instrument to instrument. Moreover, one wouldneed to create their own calibration curve with the polymer compositionof interest and also in a similar molecular weight range as thefractions. There is a slight molecular weight effect. If the calibrationcurve is obtained from similar molecular weight ranges, such effectwould be essentially negligible. In some embodiments, random ethylenecopolymers satisfy the following relationship:LnP=−237.83/T _(ATREF)+0.639T_(xo) is the ATREF temperature for a random copolymer of the samecomposition and having an ethylene mole fraction of P_(x). T_(xo) can becalculated from LnP_(x)=α/T_(xo)+β. Conversely, P_(xo) is the ethylenemole fraction for a random copolymer of the same composition and havingan ATREF temperature of T_(x), which can be calculated fromLnP_(xo)=α/T_(x)+β.

Once the block index (BI) for each preparative TREF fraction isobtained, the weight average block index, ABI, for the whole polymer canbe calculated. In some embodiments, ABI is greater than zero but lessthan about 0.3 or from about 0.1 to about 0.3. In other embodiments, ABIis greater than about 0.3 and up to about 1.0. Preferably, ABI should bein the range of from about 0.4 to about 0.7, from about 0.5 to about0.7, or from about 0.6 to about 0.9. In some embodiments, ABI is in therange of from about 0.3 to about 0.9, from about 0.3 to about 0.8, orfrom about 0.3 to about 0.7, from about 0.3 to about 0.6, from about 0.3to about 0.5, or from about 0.3 to about 0.4. In other embodiments, ABIis in the range of from about 0.4 to about 1.0, from about 0.5 to about1.0, or from about 0.6 to about 1.0, from about 0.7 to about 1.0, fromabout 0.8 to about 1.0, or from about 0.9 to about 1.0.

Another characteristic of the inventive ethylene/α-olefin interpolymeris that the inventive ethylene/α-olefin interpolymer comprises at leastone polymer fraction which can be obtained by preparative TREF, whereinthe fraction has a block index greater than about 0.1 and up to about1.0 and a molecular weight distribution, M_(w)/M_(n), greater than about1.3. In some embodiments, the polymer fraction has a block index greaterthan about 0.6 and up to about 1.0, greater than about 0.7 and up toabout 1.0, greater than about 0.8 and up to about 1.0, or greater thanabout 0.9 and up to about 1.0. In other embodiments, the polymerfraction has a block index greater than about 0.1 and up to about 1.0,greater than about 0.2 and up to about 1.0, greater than about 0.3 andup to about 1.0, greater than about 0.4 and up to about 1.0, or greaterthan about 0.4 and up to about 1.0. In still other embodiments, thepolymer fraction has a block index greater than about 0.1 and up toabout 0.5, greater than about 0.2 and up to about 0.5, greater thanabout 0.3 and up to about 0.5, or greater than about 0.4 and up to about0.5. In yet other embodiments, the polymer fraction has a block indexgreater than about 0.2 and up to about 0.9, greater than about 0.3 andup to about 0.8, greater than about 0.4 and up to about 0.7, or greaterthan about 0.5 and up to about 0.6.

For copolymers of ethylene and an α-olefin, the inventive polymerspreferably possess (1) a PDI of at least 1.3, more preferably at least1.5, at least 1.7, or at least 2.0, and most preferably at least 2.6, upto a maximum value of 5.0, more preferably up to a maximum of 3.5, andespecially up to a maximum of 2.7; (2) a heat of fusion of 80 J/g orless; (3) an ethylene content of at least 50 weight percent; (4) a glasstransition temperature, T_(g), of less than −25° C., more preferablyless than −30° C., and/or (5) one and only one T_(m).

Further, the inventive polymers can have, alone or in combination withany other properties disclosed herein, a storage modulus, G′, such thatlog (G′) is greater than or equal to 400 kPa, preferably greater than orequal to 1.0 MPa, at a temperature of 100° C. Moreover, the inventivepolymers possess a relatively flat storage modulus as a function oftemperature in the range from 0 to 100° C. (illustrated in FIG. 6) thatis characteristic of block copolymers, and heretofore unknown for anolefin copolymer, especially a copolymer of ethylene and one or moreC₃₋₈ aliphatic α-olefins. (By the term “relatively flat” in this contextis meant that log G′ (in Pascals) decreases by less than one order ofmagnitude between 50 and 100° C., preferably between 0 and 100° C.).

The inventive interpolymers may be further characterized by athermomechanical analysis penetration depth of 1 mm at a temperature ofat least 90° C. as well as a flexural modulus of from 3 kpsi (20 MPa) to13 kpsi (90 MPa). Alternatively, the inventive interpolymers can have athermomechanical analysis penetration depth of 1 mm at a temperature ofat least 104° C. as well as a flexural modulus of at least 3 kpsi (20MPa). They may be characterized as having an abrasion resistance (orvolume loss) of less than 90 mm³. FIG. 7 shows the TMA (1 mm) versusflex modulus for the inventive polymers, as compared to other knownpolymers. The inventive polymers have significantly betterflexibility-heat resistance balance than the other polymers.

Additionally, the ethylene/α-olefin interpolymers can have a melt index,I₂, from 0.01 to 2000 g/10 minutes, preferably from 0.01 to 1000 g/10minutes, more preferably from 0.01 to 500 g/10 minutes, and especiallyfrom 0.01 to 100 g/10 minutes. In certain embodiments, theethylene/α-olefin interpolymers have a melt index, I₂, from 0.01 to 10g/10 minutes, from 0.5 to 50 g/10 minutes, from 1 to 30 g/10 minutes,from 1 to 6 g/10 minutes or from 0.3 to 10 g/10 minutes. In certainembodiments, the melt index for the ethylene/α-olefin polymers is 1 g/10minutes, 3 g/10 minutes or 5 g/10 minutes.

The polymers can have molecular weights, M_(w), from 1,000 g/mole to5,000,000 g/mole, preferably from 1000 g/mole to 1,000,000, morepreferably from 10,000 g/mole to 500,000 g/mole, and especially from10,000 g/mole to 300,000 g/mole. The density of the inventive polymerscan be from 0.80 to 0.99 g/cm³ and preferably for ethylene containingpolymers from 0.85 g/cm³ to 0.97 g/cm³. In certain embodiments, thedensity of the ethylene/α-olefin polymers ranges from 0.860 to 0.925g/cm³ or 0.867 to 0.910 g/cm³.

The process of making the polymers has been disclosed in the followingpatent applications: U.S. Provisional Application No. 60/553,906, filedMar. 17, 2004; U.S. Provisional Application No. 60/662,937, filed Mar.17, 2005; U.S. Provisional Application No. 60/662,939, filed Mar. 17,2005; U.S. Provisional Application No. 60/566,2938, filed Mar. 17, 2005;PCT Application No. PCT/US2005/008916, filed Mar. 17, 2005; PCTApplication No. PCT/US2005/008915, filed Mar. 17, 2005; and PCTApplication No. PCT/US2005/008917, filed Mar. 17, 2005, all of which areincorporated by reference herein in their entirety. For example, onesuch method comprises contacting ethylene and optionally one or moreaddition polymerizable monomers other than ethylene under additionpolymerization conditions with a catalyst composition comprising:

the admixture or reaction product resulting from combining:

-   -   a. a first olefin polymerization catalyst having a high        comonomer incorporation index,    -   b. a second olefin polymerization catalyst having a comonomer        incorporation index less than 90 percent, preferably less than        50 percent, most preferably less than 5 percent of the comonomer        incorporation index of catalyst (A), and    -   c. a chain shuttling agent.        Representative catalysts and chain shuttling agent are as        follows.

Catalyst (A1) is[N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafniumdimethyl, prepared according to the teachings of WO 03/40195,2003US0204017, U.S. Ser. No. 10/429,024, filed May 2, 2003, and WO04/24740.

Catalyst (A2) is[N-(2,6-di(1-methylethyl)phenyl)amido)(2-methylphenyl)(1,2-phenylene-(6-pyridin-2-diyl)methane)]hafniumdimethyl, prepared according to the teachings of WO 03/40195,2003US0204017, U.S. Ser. No. 10/429,024, filed May 2, 2003, and WO04/24740.

Catalyst (A3) isbis[N,N′″-(2,4,6-tri(methylphenyl)amido)ethylenediamine]hafniumdibenzyl.

Catalyst (A4) isbis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)cyclohexane-1,2-diylzirconium (IV) dibenzyl, prepared substantially according to theteachings of US-A-2004/0010103.

Catalyst (B1) is1,2-bis-(3,5-di-t-butylphenylene)(1-(N-(1-methylethyl)immino)methyl)(2-oxoyl)zirconium dibenzyl

Catalyst (B2) is1,2-bis-(3,5-di-t-butylphenylene)(1-(N-(2-methylcyclohexyl)-immino)methyl)(2-oxoyl)zirconium dibenzyl

Catalyst (C1) is(t-butylamido)dimethyl(3-N-pyrrolyl-1,2,3,3a,7a-η-inden-1-yl)silanetitaniumdimethyl prepared substantially according to the techniques of U.S. Pat.No. 6,268,444:

Catalyst (C2) is(t-butylamido)di(4-methylphenyl)(2-methyl-1,2,3,3a,7a-η-inden-1-yl)silanetitaniumdimethyl prepared substantially according to the teachings ofUS-A-2003/004286:

Catalyst (C3) is(t-butylamido)di(4-methylphenyl)(2-methyl-1,2,3,3a,8a-η-s-indacen-1-yl)silanetitaniumdimethyl prepared substantially according to the teachings ofUS-A-2003/004286:

Catalyst (D1) is bis(dimethyldisiloxane)(indene-1-yl)zirconiumdichloride available from Sigma-Aldrich:

Shuttling Agents The shuttling agents employed include diethylzinc,di(1-butyl)zinc, di(n-hexyl)zinc, triethylaluminum, trioctylaluminum,triethylgallium, i-butylaluminum bis(dimethyl(t-butyl)siloxane),i-butylaluminum bis(di(trimethylsilyl)amide), n-octylaluminumdi(pyridine-2-methoxide), bis(n-octadecyl)i-butylaluminum,i-butylaluminum bis(di(n-pentyl)amide), n-octylaluminumbis(2,6-di-t-butylphenoxide, n-octylaluminum di(ethyl(1-naphthyl)amide),ethylaluminum bis(t-butyldimethylsiloxide), ethylaluminumdi(bis(trimethylsilyl)amide),-ethylaluminumbis(2,3,6,7-dibenzo-1-azacycloheptaneamide), n-octylaluminumbis(2,3,6,7-dibenzo-1-azacycloheptaneamide), n-octylaluminumbis(dimethyl(t-butyl)siloxide, ethylzinc (2,6-diphenylphenoxide), andethylzinc (t-butoxide).

Preferably, the foregoing process takes the form of a continuoussolution process for forming block copolymers, especially multi-blockcopolymers, preferably linear multi-block copolymers of two or moremonomers, more especially ethylene and a C₃₋₂₀ olefin or cycloolefin,and most especially ethylene and a C₄₋₂₀ α-olefin, using multiplecatalysts that are incapable of interconversion. That is, the catalystsare chemically distinct. Under continuous solution polymerizationconditions, the process is ideally suited for polymerization of mixturesof monomers at high monomer conversions. Under these polymerizationconditions, shuttling from the chain shuttling agent to the catalystbecomes advantaged compared to chain growth, and multi-block copolymers,especially linear multi-block copolymers are formed in high efficiency.

The inventive interpolymers may be differentiated from conventional,random copolymers, physical blends of polymers, and block copolymersprepared via sequential monomer addition, fluxional catalysts, anionicor cationic living polymerization techniques. In particular, compared toa random copolymer of the same monomers and monomer content atequivalent crystallinity or modulus, the inventive interpolymers havebetter (higher) heat resistance as measured by melting point, higher TMApenetration temperature, higher high-temperature tensile strength,and/or higher high-temperature torsion storage modulus as determined bydynamic mechanical analysis. Compared to a random copolymer containingthe same monomers and monomer content, the inventive interpolymers havelower compression set, particularly at elevated temperatures, lowerstress relaxation, higher creep resistance, higher tear strength, higherblocking resistance, faster setup due to higher crystallization(solidification) temperature, higher recovery (particularly at elevatedtemperatures), better abrasion resistance, higher retractive force, andbetter oil and filler acceptance.

The inventive interpolymers also exhibit a unique crystallization andbranching distribution relationship. That is, the inventiveinterpolymers have a relatively large difference between the tallestpeak temperature measured using CRYSTAF and DSC as a function of heat offusion, especially as compared to random copolymers containing the samemonomers and monomer level or physical blends of polymers, such as ablend of a high density polymer and a lower density copolymer, atequivalent overall density. It is believed that this unique feature ofthe inventive interpolymers is due to the unique distribution of thecomonomer in blocks within the polymer backbone. In particular, theinventive interpolymers may comprise alternating blocks of differingcomonomer content (including homopolymer blocks). The inventiveinterpolymers may also comprise a distribution in number and/or blocksize of polymer blocks of differing density or comonomer content, whichis a Schultz-Flory type of distribution. In addition, the inventiveinterpolymers also have a unique peak melting point and crystallizationtemperature profile that is substantially independent of polymerdensity, modulus, and morphology. In a preferred embodiment, themicrocrystalline order of the polymers demonstrates characteristicspherulites and lamellae that are distinguishable from random or blockcopolymers, even at PDI values that are less than 1.7, or even less than1.5, down to less than 1.3.

Moreover, the inventive interpolymers may be prepared using techniquesto influence the degree or level of blockiness. That is the amount ofcomonomer and length of each polymer block or segment can be altered bycontrolling the ratio and type of catalysts and shuttling agent as wellas the temperature of the polymerization, and other polymerizationvariables. A surprising benefit of this phenomenon is the discovery thatas the degree of blockiness is increased, the optical properties, tearstrength, and high temperature recovery properties of the resultingpolymer are improved. In particular, haze decreases while clarity, tearstrength, and high temperature recovery properties increase as theaverage number of blocks in the polymer increases. By selectingshuttling agents and catalyst combinations having the desired chaintransferring ability (high rates of shuttling with low levels of chaintermination) other forms of polymer termination are effectivelysuppressed. Accordingly, little if any β-hydride elimination is observedin the polymerization of ethylene/α-olefin comonomer mixtures accordingto embodiments of the invention, and the resulting crystalline blocksare highly, or substantially completely, linear, possessing little or nolong chain branching.

Polymers with highly crystalline chain ends can be selectively preparedin accordance with embodiments of the invention. In elastomerapplications, reducing the relative quantity of polymer that terminateswith an amorphous block reduces the intermolecular dilutive effect oncrystalline regions. This result can be obtained by choosing chainshuttling agents and catalysts having an appropriate response tohydrogen or other chain terminating agents. Specifically, if thecatalyst which produces highly crystalline polymer is more susceptibleto chain termination (such as by use of hydrogen) than the catalystresponsible for producing the less crystalline polymer segment (such asthrough higher comonomer incorporation, regio-error, or atactic polymerformation), then the highly crystalline polymer segments willpreferentially populate the terminal portions of the polymer. Not onlyare the resulting terminated groups crystalline, but upon termination,the highly crystalline polymer forming catalyst site is once againavailable for reinitiation of polymer formation. The initially formedpolymer is therefore another highly crystalline polymer segment.Accordingly, both ends of the resulting multi-block copolymer arepreferentially highly crystalline.

The ethylene α-olefin interpolymers used in the embodiments of theinvention are preferably interpolymers of ethylene with at least oneC₃-C₂₀ α-olefin. Copolymers of ethylene and a C₃-C₂₀ α-olefin areespecially preferred. The interpolymers may further comprise C₄-C₁₈diolefin and/or alkenylbenzene. Suitable unsaturated comonomers usefulfor polymerizing with ethylene include, for example, ethylenicallyunsaturated monomers, conjugated or nonconjugated dienes, polyenes,alkenylbenzenes, etc. Examples of such comonomers include C₃-C₂₀α-olefins such as propylene, isobutylene, 1-butene, 1-hexene, 1-pentene,4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, and thelike. 1-Butene and 1-octene are especially preferred. Other suitablemonomers include styrene, halo- or alkyl-substituted styrenes,vinylbenzocyclobutane, 1,4-hexadiene, 1,7-octadiene, and naphthenics(e.g., cyclopentene, cyclohexene and cyclooctene).

While ethylene/α-olefin interpolymers are preferred polymers, otherethylene/olefin polymers may also be used. Olefins as used herein referto a family of unsaturated hydrocarbon-based compounds with at least onecarbon-carbon double bond. Depending on the selection of catalysts, anyolefin may be used in embodiments of the invention. Preferably, suitableolefins are C₃-C₂₀ aliphatic and aromatic compounds containing vinylicunsaturation, as well as cyclic compounds, such as cyclobutene,cyclopentene, dicyclopentadiene, and norbornene, including but notlimited to, norbornene substituted in the 5 and 6 position with C₁-C₂₀hydrocarbyl or cyclohydrocarbyl groups. Also included are mixtures ofsuch olefins as well as mixtures of such olefins with C₄-C₄₀ diolefincompounds.

Examples of olefin monomers include, but are not limited to propylene,isobutylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene,1-nonene, 1-decene, and 1-dodecene, 1-tetradecene, 1-hexadecene,1-octadecene, 1-eicosene, 3-methyl-1-butene, 3 methyl-1-pentene,4-methyl-1-pentene, 4,6-dimethyl-1-heptene, 4-vinylcyclohexene,vinylcyclohexane, norbornadiene, ethylidene norbornene, cyclopentene,cyclohexene, dicyclopentadiene, cyclooctene, C₄-C₄₀ dienes, includingbut not limited to 1,3-butadiene, 1,3-pentadiene, 1,4-hexadiene,1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, other C₄-C₄₀ α-olefins, andthe like. In certain embodiments, the α-olefin is propylene, 1-butene,1-pentene, 1-hexene, 1-octene or a combination thereof. Although anyhydrocarbon containing a vinyl group potentially may be used inembodiments of the invention, practical issues such as monomeravailability, cost, and the ability to conveniently remove unreactedmonomer from the resulting polymer may become more problematic as themolecular weight of the monomer becomes too high.

The polymerization processes described herein are well suited for theproduction of olefin polymers comprising monovinylidene aromaticmonomers including styrene, o-methyl styrene, p-methyl styrene,t-butylstyrene, and the like. In particular, interpolymers comprisingethylene and styrene can be prepared by following the teachings herein.Optionally, copolymers comprising ethylene, styrene and a C₃-C₂₀ alphaolefin, optionally comprising a C₄-C₂₀ diene, having improved propertiescan be prepared.

Suitable non-conjugated diene monomers can be a straight chain, branchedchain or cyclic hydrocarbon diene having from 6 to 15 carbon atoms.Examples of suitable non-conjugated dienes include, but are not limitedto, straight chain acyclic dienes, such as 1,4-hexadiene, 1,6-octadiene,1,7-octadiene, 1,9-decadiene, branched chain acyclic dienes, such as5-methyl-1,4-hexadiene; 3,7-dimethyl-1,6-octadiene;3,7-dimethyl-1,7-octadiene and mixed isomers of dihydromyricene anddihydroocinene, single ring alicyclic dienes, such as1,3-cyclopentadiene; 1,4-cyclohexadiene; 1,5-cyclooctadiene and1,5-cyclododecadiene, and multi-ring alicyclic fused and bridged ringdienes, such as tetrahydroindene, methyl tetrahydroindene,dicyclopentadiene, bicyclo-(2,2,1)-hepta-2,5-diene; alkenyl, alkylidene,cycloalkenyl and cycloalkylidene norbornenes, such as5-methylene-2-norbornene (MNB); 5-propenyl-2-norbornene,5-isopropylidene-2-norbornene, 5-(4-cyclopentenyl)-2-norbornene,5-cyclohexylidene-2-norbornene, 5-vinyl-2-norbornene, and norbornadiene.Of the dienes typically used to prepare EPDMs, the particularlypreferred dienes are 1,4-hexadiene (HD), 5-ethylidene-2-norbornene(ENB), 5-vinylidene-2-norbornene (VNB), 5-methylene-2-norbornene (MNB),and dicyclopentadiene (DCPD). The especially preferred dienes are5-ethylidene-2-norbornene (ENB) and 1,4-hexadiene (HD).

One class of desirable polymers that can be made in accordance withembodiments of the invention are elastomeric interpolymers of ethylene,a C₃-C₂₀ α-olefin, especially propylene, and optionally one or morediene monomers. Preferred α-olefins for use in this embodiment of thepresent invention are designated by the formula CH₂═CHR*, where R* is alinear or branched alkyl group of from 1 to 12 carbon atoms. Examples ofsuitable α-olefins include, but are not limited to, propylene,isobutylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, and1-octene. A particularly preferred α-olefin is propylene. The propylenebased polymers are generally referred to in the art as EP or EPDMpolymers. Suitable dienes for use in preparing such polymers, especiallymulti-block EPDM type polymers include conjugated or non-conjugated,straight or branched chain-, cyclic- or polycyclic-dienes comprisingfrom 4 to 20 carbons. Preferred dienes include 1,4-pentadiene,1,4-hexadiene, 5-ethylidene-2-norbornene, dicyclopentadiene,cyclohexadiene, and 5-butylidene-2-norbornene. A particularly preferreddiene is 5-ethylidene-2-norbornene.

Because the diene containing polymers comprise alternating segments orblocks containing greater or lesser quantities of the diene (includingnone) and α-olefin (including none), the total quantity of diene andα-olefin may be reduced without loss of subsequent polymer properties.That is, because the diene and α-olefin monomers are preferentiallyincorporated into one type of block of the polymer rather than uniformlyor randomly throughout the polymer, they are more efficiently utilizedand subsequently the crosslink density of the polymer can be bettercontrolled. Such crosslinkable elastomers and the cured products haveadvantaged properties, including higher tensile strength and betterelastic recovery.

In some embodiments, the inventive interpolymers made with two catalystsincorporating differing quantities of comonomer have a weight ratio ofblocks formed thereby from 95:5 to 5:95. The elastomeric polymersdesirably have an ethylene content of from 20 to 90 percent, a dienecontent of from 0.1 to 10 percent, and an α-olefin content of from 10 to80 percent, based on the total weight of the polymer. Furtherpreferably, the multi-block elastomeric polymers have an ethylenecontent of from 60 to 90 percent, a diene content of from 0.1 to 10percent, and an α-olefin content of from 10 to 40 percent, based on thetotal weight of the polymer. Preferred polymers are high molecularweight polymers, having a weight average molecular weight (Mw) from10,000 to about 2,500,000, preferably from 20,000 to 500,000, morepreferably from 20,000 to 350,000, and a polydispersity less than 3.5,more preferably less than 3.0, and a Mooney viscosity (ML (1+4) 125° C.)from 1 to 250. More preferably, such polymers have an ethylene contentfrom 65 to 75 percent, a diene content from 0 to 6 percent, and anα-olefin content from 20 to 35 percent.

The ethylene/α-olefin interpolymers can be functionalized byincorporating at least one functional group in its polymer structure.Exemplary functional groups may include, for example, ethylenicallyunsaturated mono- and di-functional carboxylic acids, ethylenicallyunsaturated mono- and di-functional carboxylic acid anhydrides, saltsthereof and esters thereof. Such functional groups may be grafted to anethylene/α-olefin interpolymer, or it may be copolymerized with ethyleneand an optional additional comonomer to form an interpolymer ofethylene, the functional comonomer and optionally other comonomer(s).Means for grafting functional groups onto polyethylene are described forexample in U.S. Pat. Nos. 4,762,890, 4,927,888, and 4,950,541, thedisclosures of these patents are incorporated herein by reference intheir entirety. One particularly useful functional group is malicanhydride.

The amount of the functional group present in the functionalinterpolymer can vary. The functional group can typically be present ina copolymer-type functionalized interpolymer in an amount of at leastabout 1.0 weight percent, preferably at least about 5 weight percent,and more preferably at least about 7 weight percent. The functionalgroup will typically be present in a copolymer-type functionalizedinterpolymer in an amount less than about 40 weight percent, preferablyless than about 30 weight percent, and more preferably less than about25 weight percent.

Other Components

The composition can comprise at least another component, in addition tothe interpolymer, for the purposes of improving and/or controlling theviscosity, adhesive properties, shelf-life, stability and cost.Non-limiting examples of additional components include tackifiers,plasticizers (plasticizing oils or extender oils), waxes, antioxidants,UV stabilizers, colorants or pigments, fillers, flow aids, couplingagents, crosslinking agents, surfactants, solvents, and combinationsthereof. Some components for adhesive compositions have been describedin U.S. Pat. Nos. 5,750,623 and 5,143,968, both of which areincorporated herein by reference, all of which can be used inembodiments of the invention with or without modifications.

In some embodiments, the compositions disclosed herein can comprise atackifier or tackifying resin or tackifier resin. The tackifier maymodify the properties of the composition such as viscoelastic properties(e.g., tan delta), rheological properties (e.g., viscosity), tackiness(i.e., ability to stick), pressure sensitivity, and wetting property. Insome embodiments, the tackifier is used to improve the tackiness of thecomposition. In other embodiments, the tackifier is used to reduce theviscosity of the composition. In further embodiments, the tackifier isused to render the composition a pressure-sensitive adhesive. Inparticular embodiments, the tackifier is used to wet out adherentsurfaces and/or improve the adhesion to the adherent surfaces.

Any tackifier known to a person of ordinary skill in the art may be usedin the adhesion composition disclosed herein. Tackifiers suitable forthe compositions disclosed herein can be solids, semi-solids, or liquidsat room temperature. Non-limiting examples of tackifiers include (1)natural and modified rosins (e.g., gum rosin, wood rosin, tall oilrosin, distilled rosin, hydrogenated rosin, dimerized rosin, andpolymerized rosin); (2) glycerol and pentaerythritol esters of naturaland modified rosins (e.g., the glycerol ester of pale, wood rosin, theglycerol ester of hydrogenated rosin, the glycerol ester of polymerizedrosin, the pentaerythritol ester of hydrogenated rosin, and thephenolic-modified pentaerythritol ester of rosin); (3) copolymers andterpolymers of natured terpenes (e.g., styrene/terpene and alpha methylstyrene/terpene); (4) polyterpene resins and hydrogenated polyterpeneresins; (5) phenolic modified terpene resins and hydrogenatedderivatives thereof (e.g., the resin product resulting from thecondensation, in an acidic medium, of a bicyclic terpene and a phenol);(6) aliphatic or cycloaliphatic hydrocarbon resins and the hydrogenatedderivatives thereof (e.g., resins resulting from the polymerization ofmonomers consisting primarily of olefins and diolefins); (7) aromatichydrocarbon resins and the hydrogenated derivatives thereof; (8)aromatic modified aliphatic or cycloaliphatic hydrocarbon resins and thehydrogenated derivatives thereof; and combinations thereof. The amountof the tackifier in the composition can be from about 5 to about 70 wt%, from about 10 to about 65 wt %, or from about 15 to about 60 wt % ofthe total weight of the composition.

In other embodiments, the tackifiers include rosin-based tackifiers(e.g. AQUATAC® 9027, AQUATAC® 4188, SYLVALITE®, SYLVATAC® and SYLVAGUM®(rosin esters from Arizona Chemical, Jacksonville, Fla.). In otherembodiments, the tackifiers include polyterpenes or terpene resins(e.g., SYLVARES® terpene resins from Arizona Chemical, Jacksonville,Fla.). In other embodiments, the tackifiers include aliphatichydrocarbon resins such as resins resulting from the polymerization ofmonomers consisting of olefins and diolefins (e.g., ESCOREZ® 1310LC,ESCOREZ® 2596 from ExxonMobil Chemical Company, Houston, Tex.) and thehydrogenated derivatives thereof; alicyclic petroleum hydrocarbon resinsand the hydrogenated derivatives thereof (e.g. ESCOREZ® 5300 and 5400series from ExxonMobil Chemical Company; EASTOTAC® resins from EastmanChemical, Kingsport, Tenn.). In further embodiments, the tackifiers aremodified with tackifier modifiers including aromatic compounds (e.g.,ESCOREZ® 2596 from ExxonMobil Chemical Company.) and low softening pointresins (e.g., AQUATAC 5527 from Arizona Chemical, Jacksonville, Fla.).In some embodiments, the tackifier is an aliphatic hydrocarbon resinhaving at least five carbon atoms. In other embodiments, the tackifierhas a Ring and Ball (R&B) softening point equal to or greater than 80°C. The Ring and Ball (R&B) softening point can be measured by the methoddescribed in ASTM E28, which is incorporated herein by reference.

In some embodiments, the performance characteristics of the tackifier inthe composition disclosed herein can be directly related to itscompatibility with the ethylene/α-olefin interpolymer. Preferably, thecompositions with desirable adhesive properties can be obtained withtackifiers that are compatible with the interpolymer. For example, whena compatible tackifier is added in the correct concentration to theinterpolymer, desirable tack properties can be produced. Althoughincompatible tackifiers may not produce desirable tack properties, theymay be used to impact other desirable properties. For example, theproperties of the composition can be fine-tuned by the addition of atackifier having limited compatibility to reduce the tack level and/orincrease the cohesive strength characteristics.

In further embodiments, the compositions disclosed herein optionally cancomprise a plasticizer or plasticizing oil or an extender oil that mayreduce viscosity and/or improve tack properties. Any plasticizer knownto a person of ordinary skill in the art may be used in the adhesioncomposition disclosed herein. Non-limiting examples of plasticizersinclude olefin oligomers, low molecular weight polyolefins such asliquid polybutene, phthalates, mineral oils such as naphthenic,paraffinic, or hydrogenated (white) oils (e.g. Kaydol oil), vegetableand animal oil and their derivatives, petroleum derived oils, andcombinations thereof. In some embodiments, the plasticizers includepolypropylene, polybutene, hydrogenated polyisoprene, hydrogenatedpolybutadiene, polypiperylene and copolymers of piperylene and isoprene,and the like having average molecular weights between about 350 andabout 10,000. In other embodiments, the plasticizers include glycerylesters of the usual fatty acids and polymerization products thereof.

In some embodiments, a suitable insoluble plasticizer may be selectedfrom the group which includes dipropylene glycol dibenzoate,pentaerythritol tetrabenzoate; polyethylene glycol400-di-2-ethylhexoate; 2-ethylhexyl diphenyl phsophate; butyl benzylphthalate, dibutyl phthalate, dioctyl phthalate, various substitutedcitrates, and glycerates. Suitable dipropylene glycol dibenzoate andpentaerythritol tetrabenzoate may be purchased from Velsicol ChemicalCompany of Chicago, Ill. under the trade designations “Benzoflex 9-88and S-552”, respectively. Further, a suitable polyethylene glycol400-di-2-ethylhexoate may be purchased from C.P. Hall Company ofChicago, Ill. under the trade designation “Tegmer 809”. A suitable2-ethylhexyl diphenyl phosphate, and a butyl benzyl phthalate may bepurchased from Monsanto Industrial Chemical Company of St. Louis, Mo.under the trade designation “Santicizer 141 and 160”, respectively. WhenBenzoflex is used as a plasticizer in an adhesive composition, it candelay the crystallization in diaper core stabilization adhesives, whichare used to stabilize the thinner cores of diapers and adultincontinence products.

In further embodiments, the compositions disclosed herein optionally cancomprise a wax that may reduce the melt viscosity in addition toreducing costs. Any wax known to a person of ordinary skill in the artcan be used in the adhesion composition disclosed herein. Non-limitingexamples of suitable waxes include petroleum waxes, polyolefin waxessuch as low molecular weight polyethylene or polypropylene, syntheticwaxes, paraffin and microcrystalline waxes having melting points fromabout 55 to about 110° C., Fischer-Tropsch waxes and combinationsthereof. In some embodiments, the wax is a low molecular weightpolyethylene homopolymer or interpolymer having a number averagemolecular weight of about 400 to about 6,000 g/mole. In particular, theinventive interpolymer having such an average molecular weight can beused as a wax, in addition to the higher molecular weight inventivepolymer being used as a polymeric component. Where used, the amount ofthe wax in the composition can be from greater than 0 to about 50 wt %,from about 10 to about 45 wt %, or from about 25 to about 40 wt % of thetotal weight of the composition.

In further embodiments, the compositions disclosed herein optionally cancomprise an antioxidant or a stabilizer. Any antioxidant known to aperson of ordinary skill in the art may be used in the adhesioncomposition disclosed herein. Non-limiting examples of suitableantioxidants include amine-based antioxidants such as alkyldiphenylamines, phenyl-α-naphthylamine, alkyl or aralkyl substitutedphenyl-α-naphthylamine, alkylated p-phenylene diamines,tetramethyl-diaminodiphenylamine and the like; and hindered phenolcompounds such as 2,6-di-t-butyl-4-methylphenol;1,3,5-trimethyl-2,4,6-tris(3′,5′-di-t-butyl-4′-hydroxybenzyl)benzene;tetrakis[(methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)]methane(e.g., IRGANOX™ 1010, from Ciba Geigy, N.Y.);octadecyl-3,5-di-t-butyl-4-hydroxycinnamate (e.g., IRGANOX™ 1076,commercially available from Ciba Geigy) and combinations thereof. Whereused, the amount of the antioxidant in the composition can be from aboutgreater than 0 to about 1 wt %, from about 0.05 to about 0.75 wt %, orfrom about 0.1 to about 0.5 wt % of the total weight of the composition.

In further embodiments, the compositions disclosed herein optionally cancomprise an UV stabilizer that may prevent or reduce the degradation ofthe compositions by UV radiation. Any UV stabilizer known to a person ofordinary skill in the art may be used in the adhesion compositiondisclosed herein. Non-limiting examples of suitable UV stabilizersinclude benzophenones, benzotriazoles, aryl esters, oxanilides, acrylicesters, Formamidine carbon black, hindered amines, nickel quenchers,hindered amines, phenolic antioxidants, metallic salts, zinc compoundsand combinations thereof. Where used, the amount of the UV stabilizer inthe composition can be from about greater than 0 to about 1 wt %, fromabout 0.05 to about 0.75 wt %, or from about 0.1 to about 0.5 wt % ofthe total weight of the composition.

In further embodiments, the compositions disclosed herein optionally cancomprise a colorant or pigment. Any colorant or pigment known to aperson of ordinary skill in the art may be used in the adhesioncomposition disclosed herein. Non-limiting examples of suitablecolorants or pigments include inorganic pigments such as titaniumdioxide and carbon black, phthalocyanine pigments, and other organicpigments such as IRGAZIN®, CROMOPHTAL®, MONASTRAL®, CINQUASIA®,IRGALITE®, ORASOL®, all of which are available from Ciba SpecialtyChemicals, Tarrytown, N.Y. Where used, the amount of the colorant orpigment in the composition can be from about greater than 0 to about 10wt %, from about 0.1 to about 5 wt %, or from about 0.5 to about 2 wt %of the total weight of the composition.

In further embodiments, the compositions disclosed herein optionally cancomprise a filler. Any filler known to a person of ordinary skill in theart may be used in the adhesion composition disclosed herein.Non-limiting examples of suitable fillers include sand, talc, dolomite,calcium carbonate, clay, silica, mica, wollastonite, feldspar, aluminumsilicate, alumina, hydrated alumina, glass bead, glass microsphere,ceramic microsphere, thermoplastic microsphere, barite, wood flour, andcombinations thereof. Where used, the amount of the filler in thecomposition can be from about greater than 0 to about 60 wt %, fromabout 1 to about 50 wt %, or from about 5 to about 40 wt % of the totalweight of the composition.

In formulating the composition, it is preferable that each of theadditives are compatible with the ethylene/α-olefin interpolymerdisclosed herein so that the additives do not phase separate from theethylene/α-olefin interpolymer, particularly in molten state. Ingeneral, the compatibility of an additive with the ethylene/α-olefininterpolymer increases with a decrease in the difference between theirsolubility parameters such as Hildebrand solubility parameters. SomeHildebrand solubility parameters are tabulated for solvents in: Barton,A. F. M., Handbook of Solubility and Other Cohesion Parameters, 2nd Ed.CRC Press, Boca Raton, Fla. (1991); for monomers and representativepolymers in Polymer Handbook, 3rd Ed., J. Brandrup & E. H. Immergut,Eds. John Wiley, NY, pages 519-557 (1989); and for many commerciallyavailable polymers in Barton, A. F. M., Handbook of Polymer-LiquidInteraction Parameters and Solubility Parameters, CRC Press, Boca Raton,Fla. (1990), all of which are incorporated herein by reference. TheHildebrand solubility parameter for a copolymer may be calculated usinga volume fraction weighting of the individual Hildebrand solubilityparameters for each monomer comprising the copolymer, as described forbinary copolymers in Barton A. F. M., Handbook of Solubility Parametersand Other Cohesion Parameters, CRC Press, Boca Raton, page 12 (1990).The magnitude of the Hildebrand solubility parameter for polymericmaterials is also known to be weakly dependent upon the molecular weightof the polymer, as noted in Barton, pages 446-448. Therefore, there willbe a preferred molecular weight range for a given ethylene/α-olefininterpolymer, and adhesive strength may be additionally controlled bymanipulating the molecular weight of the ethylene/α-olefin interpolymeror the additives such as the tackifier. In some embodiments, theabsolute difference in Hildebrand solubility parameter between theethylene/α-olefin interpolymer and an additive such as the tackifier,plasticizer or oil, and the wax falls within the range of greater than 0to about 10 MPa^(1/2), about 0.1 to about 5 MPa^(1/2), about 0.5 toabout 4.0 MPa^(1/2), or about 1 to about 3.0 MPa^(1/2).

The compatibility of the additives with the ethylene/α-olefininterpolymer can also be determined by cloud point measurement anddynamic mechanical analysis. The cloud point temperature is thetemperature at which a component begins to solidify or “cloud up” as itcools from a clear liquid phase to the solid phase. For example, forwaxes, the cloud point is usually close to the melting point of the wax.Generally, the lower the cloud point temperature, the greater thecompatibility. The cloud point measurement is disclosed in “Adhesivesand Coatings Manual” by National Distillers and Chemical Corporation(1983), which is incorporated herein by reference.

Dynamic mechanical analysis (DMA) can be another technique to identifycompatibility characteristics of the additives with theethylene/α-olefin interpolymer. When an additive, such as the tackifierhaving a first glass transition temperature (Tg), is compatible with theethylene/α-olefin interpolymer having a second Tg, DMA generally revealsone single glass transition zone but with the second Tg shift to adifferent temperature due to the contribution of the first Tg. Thisindicates an intimate mix (solubility) between the tackifier and theethylene/α-olefin interpolymer. In case of incompatibility, DMA candetect a separate phase transition for each of the tackifier and theethylene/α-olefin interpolymer.

Preparation of Compositions Comprising Ethylene/α-Olefin Interpolymers

In some embodiments, the compositions disclosed herein are adhesiveand/or thermoplastic marking compositions comprising anethylene/α-olefin interpolymer, a tackifier and optional otheradditives. The blending of the ethylene/α-olefin interpolymer with theadditives can be done by any known method that can result in asubstantially homogeneous distribution of the components of theadhesive. The ingredients of the compositions can be blended usingmethods known to a person of ordinary skill in the art. Non-limitingexamples of suitable blending methods include melt blending, solventblending, and the like.

In some embodiments, the ingredients of the compositions are meltblended by a method as described by Guerin et al. in U.S. Pat. No.4,152,189. That is, all solvent (if used) is removed from theingredients by heating to an appropriate elevated temperature of about100° C. to about 200° C. or about 150° C. to about 175° C. at a pressureof about 5 Torr to about 10 Torr. Then, the ingredients are weighed intoa vessel in the desired proportions. The blend is then formed by heatingthe contents of the vessel to about 150° C. to about 175° C. whilestirring.

In other embodiments, the ingredients of the compositions are processedusing solvent blending. The ingredients in the blend are substantiallysoluble in the solvents used.

Physical blending devices that provide dispersive mixing, distributivemixing, or a combination of dispersive and distributive mixing can beuseful in preparing homogenous blends. Both batch and continuous methodsof physical blending can be used. Non-limiting examples of batch methodsinclude those methods using BRABENDER® mixing equipment (e.g., BRABENDERPREP CENTERS®, available from C. W. Brabender Instruments, Inc., SouthHackensack, N.J.) or BANBURY® internal mixing and roll milling(available from Farrel Company, Ansonia, Conn.) equipment. Non-limitingexamples of continuous methods include single screw extruding, twinscrew extruding, disk extruding, reciprocating single screw extruding,and pin barrel single screw extruding.

An aqueous dispersion of the ethylene/α-olefin interpolymer may also beused in the formulation of various compositions. U.S. Pat. No.5,574,091, incorporated by reference herein in its entirety, teaches thepreparation of aqueous dispersions of olefin copolymers in the presenceof a stabilizing and an emulsifying amount of a suitable surfactant,such as sulfate of an ethoxylated phenol, e.g.,poly(oxy-1,2-ethanediyl)α-sulfo-ω(nonylphonoxy) ammonium salt. Suchmethods can also be used to make aqueous dispersions of theethylene/α-olefin interpolymer. Additional suitable methods aredisclosed in U.S. Pat. No. 5,539,021, which is incorporated by referenceherein in its entirety.

Applications of Compositions Comprising Ethylene/α-Olefin Interpolymers

The compositions disclosed herein can be used as hot melt adhesives,pressure sensitive adhesives or as thermoplastic marking compositions.It can be applied to manufacture any article that requires or comprisesa hot melt adhesive or a pressure sensitive adhesive. Non-limitingexamples of suitable articles include paper products, packagingmaterials, laminated wood panels, kitchen countertops, vehicles, labels,disposable diapers, hospital pads, feminine sanitary napkins, surgicaldrapes, tapes, cases, cartons, trays, medical devices, and bandages. Ina further embodiment, the adhesive composition can be used in tapes,cases, cartons, trays, medical devices, and bandages.

In some embodiments, the compositions are used as hot melt adhesives.Such hot melt adhesive compositions can be used in industrialapplications including packaging, particularly for low temperature usesuch as for dairy products or for freezer packaging of food products,and in sanitary disposable consumer articles, for example, diapers,feminine care pads, napkins, and the like. Some other suitableapplications include book-binding, wood working and labeling.

In other embodiments, the compositions disclosed herein may be used asPSAs. Such PSA adhesive compositions can be applied to sheeting products(e.g., decorative, reflective, and graphical), labelstock, and tapebackings. The substrate can be any suitable type of material dependingon the desired application. In certain embodiments, the substratecomprises a nonwoven, paper, polymeric film (e.g., polypropylene (e.g.,biaxially oriented polypropylene (BOPP)), polyethylene, polyurea, orpolyester (e.g., polyethylene terephthalate (PET)), or release liner(e.g., siliconized liner).

In still other embodiments, the compositions can be utilized to formtape. For example, the PSA or hot melt adhesive composition is appliedto at least one side of the backing of the tape. The adhesivecomposition may then be crosslinked to further improve its shearstrength. Any suitable crosslinking method (e.g., exposure to radiation,such as ultraviolet or electron beam) or crosslinker additive (e.g.,phenolic and silane curatives) may be utilized.

The adhesive compositions disclosed herein may be applied to the desiredsubstrate or adhered in any manner known in the art, particularly thosemethods used traditionally for making tapes, cases, cartons, trays,medical devices, and bandages. In other embodiments, the adhesivecompositions can be applied by a coating head or nozzle, with associatedequipment. The adhesive compositions can be applied as fine lines, dotsor spray coatings, in addition to other traditional forms as desired.

In some embodiments, the adhesive compositions can be applied using meltextrusion techniques. The adhesive composition can be applied by eithercontinuous or batch processes. An example of a batch process is theplacement of a portion of the adhesive composition between a substrateto which the adhesive composition is to be adhered and a surface capableof releasing the adhesive to form a composite structure. An example of acontinuous forming method includes drawing the adhesive composition outof a heated film die and subsequently contacting the drawn compositionto a moving plastic web or other suitable substrate.

In other embodiments, the adhesive compositions can be coated using asolvent-based method. For example, the solvent-based adhesivecomposition can be coated by such methods as knife coating, rollcoating, gravure coating, rod coating, curtain coating, and air knifecoating. The coated solvent-based adhesive composition is then dried toremove the solvent. Preferably, the applied solvent-based adhesivecomposition is subjected to elevated temperatures, such as thosesupplied by an oven, to expedite drying.

In some embodiments, the compositions disclosed herein are used asthermoplastic marking compositions for marking roads. The thermoplasticmarking compositions can be in the form of a hot melt extrusion roadmarking, hot melt spray road marking, hot melt hand applied roadmarking, colored hot melt marked bicycle lane, simulation or trainingroad marking, preformed extruded traffic symbol or tape, flexible andsoft sports/playground surface marking, safety marking on a ship, or areflective traffic safety coating. The general formulations anddescriptions of thermoplastic marking compositions have been disclosedin U.S. Pat. No. 6,552,110, which is incorporated herein by reference.In particular embodiments, the thermoplastic marking compositionscomprise the ethylene/α-olefin interpolymer disclosed herein, atackifier, a filler and optionally a pigment. Preferably, the filler isglass beads or glass microspheres.

The filler will be provided to the thermoplastic marking composition inan amount of from 40 to 90 weight percent, preferably from 50 to 90weight percent. In particularly preferred embodiments, the filler willcomprise a combination of the following: 0 to 60 weight percent sand, 0to 100 percent dolomite or talc, 0 to 50 weight percent glassmicrospheres, and 1 to 20 weight percent pigment.

When it is desired that the thermoplastic coating composition havereflective attributes, a reflective inorganic filler will be employed.One particularly preferred reflective inorganic filler is glassmicrospheres. When a reflective inorganic filler is employed, it willtypically be provided to the thermoplastic coating composition in anamount of at least 5 weight percent, preferably at least 10 weightpercent, and more preferably at least 20 weight percent. The reflectiveinorganic filler will be provided to the thermoplastic coatingcomposition in an amount of no more than 70, preferably no more than 50weight percent, and most preferably no more than 40 weight percent.

Certain inorganic fillers will typically be employed in an effort toreduce the cost of the formulation. One suitable extending filler isdolomite clay. When employed, the dolomite filler will be provided in anamount of at least 10 weight percent, more preferably at least 20 weightpercent, and most preferably at least 30 weight percent of thethermoplastic coating composition. The dolomite filler will typically beprovided in an amount of no more than 80 weight percent, more preferablyno more than 75 weight percent, and most preferably no more than 70weight percent of the thermoplastic coating composition.

The thermoplastic marking compositions are advantageous in that they maybe readily designed to be applied by the various techniques used in theindustry. For instance, it is now possible to develop a singleformulation, which may be usefully applied by extrusion, screed, orspray techniques.

The thermoplastic marking compositions will preferably exhibit anadhesion, as measured in accordance with the techniques set forth inExample Two of U.S. Pat. No. 6,552,110, of at least 1.0 N/mm²,preferably at least 1.2 N/mm², more preferably at least 1.3 N/mm², andmost preferably at least 1.5 N/mm². U.S. Pat. No. 6,552,110 isincorporated herein by reference.

The thermoplastic marking compositions will preferably exhibit aluminance factor, as measured in accordance with the techniques setforth in Example Two of U.S. Pat. No. 6,552,110, of at least 70,preferably at least 75, more preferably at least 76, and most preferablyat least 78.

The thermoplastic marking compositions further exhibit good lowtemperature abrasion resistance. The subject formulations exhibitimproved low temperature flexibility and low temperature adhesion, andexhibit improved smoke and low odor properties at high temperatures. Thesubject formulations exhibit a broad potential range of applicationtemperatures, particularly at temperatures of from 150° C. to 250° C.,which makes them suitable for application by different means. Forinstance, the ability of the compositions to be applied at lowerapplication temperatures, that is, temperatures of about 150 to 170° C.,makes them suitable for application by extrusion coating techniques;while the ability of the compositions to be applied at higherapplication temperatures, that is, temperatures of 200° C. to 250° C.makes them suitable for application by spray coating techniques. Thesubject formulations are preferably resistant to dirt pick-up, andfurther preferably exhibit less viscosity variability relative tosystems which lack the homogeneous ethylene polymer.

The subject formulations are usefully applied via spray, screed, andextrusion techniques. In addition, the subject formulations may beprovided as preformed tapes, which are laid upon the surface and bondedto it by heating with, for example, a gas flame, optionally under someapplied pressure, as by rolling.

Exemplary applications for the thermoplastic marking compositions are inhot melt extrusion road marking; hot melt spray road marking; hot melthand applied road markings; colored hot melt marked bicycle lanesapplied by spray or extrusion; marking of simulation/training roads foricy surface driving; preformed extruded traffic symbols (such as arrows,letters, etc.) and tapes (such as for traffic safety, information,decoration, etc.) (also called premarks or hot melt tapes); marking offlexible and soft sports/playground surfaces, such as tartan (forinstance, in the marking of tennis courts, outdoor and indoor sportsfloorings, etc.); safety markings on ships, oil rigs, etc.; andreflecting traffic safety coatings for tunnels, concrete, metals withglass beads or other reflecting/self-glowing pigments.

In one preferred application, the subject thermoplastic markingcompositions will be employed in embossed road markings. Embossed roadmarkings are formed by extrusion of a marking composition onto asurface; applying reflective particles, such as glass beads, to theextruded marking; and embossing the extruded marking such as to createchannels or other ridges. Such embossed markings are desirable, in thatthey provide enhanced water drainage and improve nighttime reflectiveproperties, particularly in rainy weather. The thermoplastic markingcompositions of the invention are advantageous in embossed road markingapplications, as they provide the requisite degree of flexibility,adhesion, and abrasion, even under cold temperature conditions.

The following examples are presented to exemplify embodiments of theinvention but are not intended to limit the invention to the specificembodiments set forth. Unless indicated to the contrary, all parts andpercentages are by weight. All numerical values are approximate. Whennumerical ranges are given, it should be understood that embodimentsoutside the stated ranges may still fall within the scope of theinvention. Specific details described in each example should not beconstrued as necessary features of the invention.

Testing Methods

In the examples that follow, the following analytical techniques areemployed:

GPC Method for Samples 1-4 and A-C

An automated liquid-handling robot equipped with a heated needle set to160° C. is used to add enough 1,2,4-trichlorobenzene stabilized with 300ppm Ionol to each dried polymer sample to give a final concentration of30 mg/mL. A small glass stir rod is placed into each tube and thesamples are heated to 160° C. for 2 hours on a heated, orbital-shakerrotating at 250 rpm. The concentrated polymer solution is then dilutedto 1 mg/ml using the automated liquid-handling robot and the heatedneedle set to 160° C.

A Symyx Rapid GPC system is used to determine the molecular weight datafor each sample. A Gilson 350 pump set at 2.0 ml/min flow rate is usedto pump helium-purged 1,2-dichlorobenzene stabilized with 300 ppm Ionolas the mobile phase through three Plgel 10 micrometer (μm) Mixed B 300mm×7.5 mm columns placed in series and heated to 160° C. A Polymer LabsELS 1000 Detector is used with the Evaporator set to 250° C., theNebulizer set to 165° C., and the nitrogen flow rate set to 1.8 SLM at apressure of 60-80 psi (400-600 kPa) N₂. The polymer samples are heatedto 160° C. and each sample injected into a 250 μl loop using theliquid-handling robot and a heated needle. Serial analysis of thepolymer samples using two switched loops and overlapping injections areused. The sample data is collected and analyzed using Symyx Epoch™software. Peaks are manually integrated and the molecular weightinformation reported uncorrected against a polystyrene standardcalibration curve.

Standard CRYSTAF Method

Branching distributions are determined by crystallization analysisfractionation (CRYSTAF) using a CRYSTAF 200 unit commercially availablefrom PolymerChar, Valencia, Spain. The samples are dissolved in 1,2,4trichlorobenzene at 160° C. (0.66 mg/mL) for 1 hr and stabilized at 95°C. for 45 minutes. The sampling temperatures range from 95 to 30° C. ata cooling rate of 0.2° C./min. An infrared detector is used to measurethe polymer solution concentrations. The cumulative solubleconcentration is measured as the polymer crystallizes while thetemperature is decreased. The analytical derivative of the cumulativeprofile reflects the short chain branching distribution of the polymer.

The CRYSTAF peak temperature and area are identified by the peakanalysis module included in the CRYSTAF Software (Version 2001.b,PolymerChar, Valencia, Spain). The CRYSTAF peak finding routineidentifies a peak temperature as a maximum in the dW/dT curve and thearea between the largest positive inflections on either side of theidentified peak in the derivative curve. To calculate the CRYSTAF curve,the preferred processing parameters are with a temperature limit of 70°C. and with smoothing parameters above the temperature limit of 0.1, andbelow the temperature limit of 0.3.

DSC Standard Method (Excluding Samples 1-4 and A-C)

Differential Scanning Calorimetry results are determined using a TAImodel Q1000 DSC equipped with an RCS cooling accessory and anautosampler. A nitrogen purge gas flow of 50 ml/min is used. The sampleis pressed into a thin film and melted in the press at about 175° C. andthen air-cooled to room temperature (25° C.). 3-10 mg of material isthen cut into a 6 mm diameter disk, accurately weighed, placed in alight aluminum pan (ca 50 mg), and then crimped shut. The thermalbehavior of the sample is investigated with the following temperatureprofile. The sample is rapidly heated to 180° C. and held isothermal for3 minutes in order to remove any previous thermal history. The sample isthen cooled to −40° C. at 10° C./min cooling rate and held at −40° C.for 3 minutes. The sample is then heated to 150° C. at 10° C./min.heating rate. The cooling and second heating curves are recorded.

The DSC melting peak is measured as the maximum in heat flow rate (W/g)with respect to the linear baseline drawn between −30° C. and end ofmelting. The heat of fusion is measured as the area under the meltingcurve between −30° C. and the end of melting using a linear baseline.

GPC Method (Excluding Samples 1-4 and A-C)

The gel permeation chromatographic system consists of either a PolymerLaboratories Model PL-210 or a Polymer Laboratories Model PL-220instrument. The column and carousel compartments are operated at 140° C.Three Polymer Laboratories 10-micron Mixed-B columns are used. Thesolvent is 1,2,4 trichlorobenzene. The samples are prepared at aconcentration of 0.1 grams of polymer in 50 milliliters of solventcontaining 200 ppm of butylated hydroxytoluene (BHT). Samples areprepared by agitating lightly for 2 hours at 160° C. The injectionvolume used is 100 microliters and the flow rate is 1.0 ml/minute.

Calibration of the GPC column set is performed with 21 narrow molecularweight distribution polystyrene standards with molecular weights rangingfrom 580 to 8,400,000, arranged in 6 “cocktail” mixtures with at least adecade of separation between individual molecular weights. The standardsare purchased from Polymer Laboratories (Shropshire, UK). Thepolystyrene standards are prepared at 0.025 grams in 50 milliliters ofsolvent for molecular weights equal to or greater than 1,000,000, and0.05 grams in 50 milliliters of solvent for molecular weights less than1,000,000. The polystyrene standards are dissolved at 80° C. with gentleagitation for 30 minutes. The narrow standards mixtures are run firstand in order of decreasing highest molecular weight component tominimize degradation. The polystyrene standard peak molecular weightsare converted to polyethylene molecular weights using the followingequation (as described in Williams and Ward, J. Polym. Sci., Polym.Let., 6, 621 (1968)):M _(polyethylene)=0.431(M _(polystyrene)).

Polyethylene equivalent molecular weight calculations are performedusing Viscotek TriSEC software Version 3.0.

Compression Set

Compression set is measured according to ASTM D 395. The sample isprepared by stacking 25.4 mm diameter round discs of 3.2 mm, 2.0 mm, and0.25 mm thickness until a total thickness of 12.7 mm is reached. Thediscs are cut from 12.7 cm×12.7 cm compression molded plaques moldedwith a hot press under the following conditions: zero pressure for 3 minat 190° C., followed by 86 MPa for 2 min at 190° C., followed by coolinginside the press with cold running water at 86 MPa.

Density

Samples for density measurement are prepared according to ASTM D 1928.Measurements are made within one hour of sample pressing using ASTMD792, Method B.

Flexural/Secant Modulus/Storage Modulus

Samples are compression molded using ASTM D 1928. Flexural and 2 percentsecant moduli are measured according to ASTM D-790. Storage modulus ismeasured according to ASTM D 5026-01 or equivalent technique.

Optical Properties

Films of 0.4 mm thickness are compression molded using a hot press(Carver Model #4095-4PR1001R). The pellets are placed betweenpolytetrafluoroethylene sheets, heated at 190° C. at 55 psi (380 kPa)for 3 min, followed by 1.3 MPa for 3 min, and then 2.6 MPa for 3 min.The film is then cooled in the press with running cold water at 1.3 MPafor 1 min. The compression molded films are used for opticalmeasurements, tensile behavior, recovery, and stress relaxation.

Clarity is measured using BYK Gardner Haze-gard as specified in ASTM D1746.

45° gloss is measured using BYK Gardner Glossmeter Microgloss 45° asspecified in ASTM D-2457

Internal haze is measured using BYK Gardner Haze-gard based on ASTM D1003 Procedure A. Mineral oil is applied to the film surface to removesurface scratches.

Mechanical Properties—Tensile, Hysteresis, and Tear

Stress-strain behavior in uniaxial tension is measured using ASTM D 1708microtensile specimens. Samples are stretched with an Instron at 500%min⁻¹ at 21° C. Tensile strength and elongation at break are reportedfrom an average of 5 specimens.

100% and 300% Hysteresis is determined from cyclic loading to 100% and300% strains using ASTM D 1708 microtensile specimens with an Instron™instrument. The sample is loaded and unloaded at 267% min⁻¹ for 3 cyclesat 21° C. Cyclic experiments at 300% and 80° C. are conducted using anenvironmental chamber. In the 80° C. experiment, the sample is allowedto equilibrate for 45 minutes at the test temperature before testing. Inthe 21° C., 300% strain cyclic experiment, the retractive stress at 150%strain from the first unloading cycle is recorded. Percent recovery forall experiments are calculated from the first unloading cycle using thestrain at which the load returned to the base line. The percent recoveryis defined as:

${\%\mspace{14mu}{Recovery}} = {\frac{ɛ_{f} - ɛ_{s}}{ɛ_{f}} \times 100}$

where ε_(f) is the strain taken for cyclic loading and ε_(s) is thestrain where the load returns to the baseline during the 1^(st)unloading cycle.

Stress relaxation is measured at 50 percent strain and 37° C. for 12hours using an Instron™ instrument equipped with an environmentalchamber. The gauge geometry was 76 mm×25 mm×0.4 mm. After equilibratingat 37° C. for 45 min in the environmental chamber, the sample wasstretched to 50% strain at 333% min⁻¹. Stress was recorded as a functionof time for 12 hours. The percent stress relaxation after 12 hours wascalculated using the formula:

${\%\mspace{14mu}{Stress}\mspace{14mu}{Relaxation}} = {\frac{L_{0} - L_{12}}{L_{0}} \times 100}$where L₀ is the load at 50% strain at 0 time and L₁₂ is the load at 50percent strain after 12 hours.

Tensile notched tear experiments are carried out on samples having adensity of 0.88 g/cc or less using an Instron™ instrument. The geometryconsists of a gauge section of 76 mm×13 mm×0.4 mm with a 2 mm notch cutinto the sample at half the specimen length. The sample is stretched at508 mm min⁻¹ at 21° C. until it breaks. The tear energy is calculated asthe area under the stress-elongation curve up to strain at maximum load.An average of at least 3 specimens are reported.

TMA

Thermal Mechanical Analysis (Penetration Temperature) is conducted on 30mm diameter×3.3 mm thick, compression molded discs, formed at 180° C.and 10 MPa molding pressure for 5 minutes and then air quenched. Theinstrument used is a TMA 7 brand available from Perkin-Elmer. In thetest, a probe with 1.5 mm radius tip (P/N N519-0416) is applied to thesurface of the sample disc with 1N force. The temperature is raised at5° C./min from 25° C. The probe penetration distance is measured as afunction of temperature. The experiment ends when the probe haspenetrated 1 mm into the sample.

DMA

Dynamic Mechanical Analysis (DMA) is measured on compression moldeddisks formed in a hot press at 180° C. at 10 MPa pressure for 5 minutesand then water cooled in the press at 90° C./min. Testing is conductedusing an ARES controlled strain rheometer (TA instruments) equipped withdual cantilever fixtures for torsion testing.

A 1.5 mm plaque is pressed and cut in a bar of dimensions 32×12 mm. Thesample is clamped at both ends between fixtures separated by 10 mm (gripseparation ΔL) and subjected to successive temperature steps from −100°C. to 200° C. (5° C. per step). At each temperature the torsion modulusG′ is measured at an angular frequency of 10 rad/s, the strain amplitudebeing maintained between 0.1 percent and 4 percent to ensure that thetorque is sufficient and that the measurement remains in the linearregime.

An initial static force of 10 g is maintained (auto-tension mode) toprevent slack in the sample when thermal expansion occurs. As aconsequence, the grip separation ΔL increases with the temperature,particularly above the melting or softening point of the polymer sample.The test stops at the maximum temperature or when the gap between thefixtures reaches 65 mm.

Melt Index

Melt index, or I₂, is measured in accordance with ASTM D 1238, Condition190° C./2.16 kg. Melt index, or I₁₀ is also measured in accordance withASTM D 1238, Condition 190° C./10 kg.

ATREF

Analytical temperature rising elution fractionation (ATREF) analysis isconducted according to the method described in U.S. Pat. No. 4,798,081and Wilde, L.; Ryle, T. R.; Knobeloch, D.C.; Peat, I. R.; Determinationof Branching Distributions in Polyethylene and Ethylene Copolymers, J.Polym. Sci., 20, 441-455 (1982), which are incorporated by referenceherein in their entirety. The composition to be analyzed is dissolved intrichlorobenzene and allowed to crystallize in a column containing aninert support (stainless steel shot) by slowly reducing the temperatureto 20° C. at a cooling rate of 0.1° C./min. The column is equipped withan infrared detector. An ATREF chromatogram curve is then generated byeluting the crystallized polymer sample from the column by slowlyincreasing the temperature of the eluting solvent (trichlorobenzene)from 20 to 120° C. at a rate of 1.5° C./min.

¹³C NMR Analysis

The samples are prepared by adding approximately 3 g of a 50/50 mixtureof tetrachloroethane-d2/orthodichlorobenzene to 0.4 g sample in a 10 mmNMR tube. The samples are dissolved and homogenized by heating the tubeand its contents to 150° C. The data are collected using a JEOL Eclipse™400 MHz spectrometer or a Varian Unity Plus™ 400 MHz spectrometer,corresponding to a 13C resonance frequency of 100.5 MHz. The data areacquired using 4000 transients per data file with a 6 second pulserepetition delay. To achieve minimum signal-to-noise for quantitativeanalysis, multiple data files are added together. The spectral width is25,000 Hz with a minimum file size of 32K data points. The samples areanalyzed at 130° C. in a 10 mm broad band probe. The comonomerincorporation is determined using Randall's triad method (Randall, J.C.; JMS-Rev. Macromol. Chem. Phys., C29, 201-317 (1989), which isincorporated by reference herein in its entirety.

Polymer Fractionation by TREF

Large-scale TREF fractionation is carried by dissolving 15-20 g ofpolymer in 2 liters of 1,2,4-trichlorobenzene (TCB) by stirring for 4hours at 160° C. The polymer solution is forced by 15 psig (100 kPa)nitrogen onto a 3 inch by 4 foot (7.6 cm×12 cm) steel column packed witha 60:40 (v:v) mix of 30-40 mesh (600-425 μm) spherical, technicalquality glass beads (available from Potters Industries, HC 30 Box 20,Brownwood, Tex., 76801) and stainless steel, 0.028″ (0.7 mm) diametercut wire shot (available from Pellets, Inc., 63 Industrial Drive, NorthTonawanda, N.Y., 14120). The column is immersed in a thermallycontrolled oil jacket, set initially to 160° C. The column is firstcooled ballistically to 125° C., then slow cooled to 20° C. at 0.04° C.per minute and held for one hour. Fresh TCB is introduced at about 65ml/min while the temperature is increased at 0.167° C. per minute.

Approximately 2000 ml portions of eluant from the preparative TREFcolumn are collected in a 16 station, heated fraction collector. Thepolymer is concentrated in each fraction using a rotary evaporator untilabout 50 to 100 ml of the polymer solution remains. The concentratedsolutions are allowed to stand overnight before adding excess methanol,filtering, and rinsing (approx. 300-500 ml of methanol including thefinal rinse). The filtration step is performed on a 3 position vacuumassisted filtering station using 5.0 μm polytetrafluoroethylene coatedfilter paper (available from Osmonics Inc., Cat# Z50WP04750). Thefiltrated fractions are dried overnight in a vacuum oven at 60° C. andweighed on an analytical balance before further testing.

Melt Strength

Melt Strength (MS) is measured by using a capillary rheometer fittedwith a 2.1 mm diameter, 20:1 die with an entrance angle of approximately45 degrees. After equilibrating the samples at 190° C. for 10 minutes,the piston is run at a speed of 1 inch/minute (2.54 cm/minute). Thestandard test temperature is 190° C. The sample is drawn uniaxially to aset of accelerating nips located 100 mm below the die with anacceleration of 2.4 mm/sec 2. The required tensile force is recorded asa function of the take-up speed of the nip rolls. The maximum tensileforce attained during the test is defined as the melt strength. In thecase of polymer melt exhibiting draw resonance, the tensile force beforethe onset of draw resonance was taken as melt strength. The meltstrength is recorded in centiNewtons (“cN”).

Catalysts

The term “overnight”, if used, refers to a time of approximately 16-18hours, the term “room temperature”, refers to a temperature of 20-25°C., and the term “mixed alkanes” refers to a commercially obtainedmixture of C₆₋₉ aliphatic hydrocarbons available under the tradedesignation Isopar E®, from ExxonMobil Chemical Company. In the eventthe name of a compound herein does not conform to the structuralrepresentation thereof, the structural representation shall control. Thesynthesis of all metal complexes and the preparation of all screeningexperiments were carried out in a dry nitrogen atmosphere using dry boxtechniques. All solvents used were HPLC grade and were dried beforetheir use.

MMAO refers to modified methylalumoxane, a triisobutylaluminum modifiedmethylalumoxane available commercially from Akzo-Noble Corporation.

The preparation of catalyst (B1) is conducted as follows.

a) Preparation of(1-methylethyl)(2-hydroxy-3,5-di(t-butyl)phenyl)methylimine

3,5-Di-t-butylsalicylaldehyde (3.00 g) is added to 10 mL ofisopropylamine. The solution rapidly turns bright yellow. After stirringat ambient temperature for 3 hours, volatiles are removed under vacuumto yield a bright yellow, crystalline solid (97 percent yield).

b) Preparation of1,2-bis-(3,5-di-t-butylnhenplene)(1-N-(1-methylethyl)immino)methyl)(2-oxoyl)zirconiumdibenzyl

A solution of (1-methylethyl)(2-hydroxy-3,5-di(t-butyl)phenyl)imine (605mg, 2.2 mmol) in 5 mL toluene is slowly added to a solution ofZr(CH₂Ph)₄ (500 mg, 1.1 mmol) in 50 mL toluene. The resulting darkyellow solution is stirred for 30 min. Solvent is removed under reducedpressure to yield the desired product as a reddish-brown solid.

The preparation of catalyst (B2) is conducted as follows.

a) Preparation of(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)imine

2-Methylcyclohexylamine (8.44 mL, 64.0 mmol) is dissolved in methanol(90 mL), and di-t-butylsalicaldehyde (10.00 g, 42.67 mmol) is added. Thereaction mixture is stirred for three hours and then cooled to −25° C.for 12 hrs. The resulting yellow solid precipitate is collected byfiltration and washed with cold methanol (2×15 mL), and then dried underreduced pressure. The yield is 11.17 g of a yellow solid. ¹H NMR isconsistent with the desired product as a mixture of isomers.

b) Preparation ofbis-(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)immino)zirconium dibenzyl

A solution of(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)imine (7.63g, 23.2 mmol) in 200 mL toluene is slowly added to a solution ofZr(CH₂Ph)₄ (5.28 g, 11.6 mmol) in 600 mL toluene. The resulting darkyellow solution is stirred for 1 hour at 25° C. The solution is dilutedfurther with 680 mL toluene to give a solution having a concentration of0.00783 M.

Cocatalyst 1 A mixture of methyldi(C₁₄₋₁₈ alkyl)ammonium salts oftetrakis(pentafluorophenyl)borate (here-in-after armeenium borate),prepared by reaction of a long chain trialkylamine (Armeen™ M2HT,available from Akzo-Nobel, Inc.), HCl and Li[B(C₆F₅)₄], substantially asdisclosed in U.S. Pat. No. 5,919,9883, Ex. 2.

Cocatalyst 2 Mixed C₁₄₋₁₈ alkyldimethylammonium salt ofbis(tris(pentafluorophenyl)-alumane)-2-undecylimidazolide, preparedaccording to U.S. Pat. No. 6,395,671, Ex. 16.

Shuttling Agents The shuttling agents employed include diethylzinc (DEZ,SA1), di(i-butyl)zinc (SA2), di(n-hexyl)zinc (SA3), triethylaluminum(TEA, SA4), trioctylaluminum (SA5), triethylgallium (SA6),i-butylaluminum bis(dimethyl(t-butyl)siloxane) (SA7), i-butylaluminumbis(di(trimethylsilyl)amide) (SA8), n-octylaluminumdi(pyridine-2-methoxide) (SA9), bis(n-octadecyl)i-butylaluminum (SA 10),i-butylaluminum bis(di(n-pentyl)amide) (SA 11), n-octylaluminumbis(2,6-di-t-butylphenoxide) (SA12), n-octylaluminumdi(ethyl(1-naphthyl)amide) (SA13), ethylaluminumbis(t-butyldimethylsiloxide) (SA14), ethylaluminumdi(bis(trimethylsilyl)amide) (SA15), ethylaluminumbis(2,3,6,7-dibenzo-1-azacycloheptaneamide) (SA 16), n-octylaluminumbis(2,3,6,7-dibenzo-1-azacycloheptaneamide) (SA 17), n-octylaluminumbis(dimethyl(t-butyl)siloxide (SA18), ethylzinc (2,6-diphenylphenoxide)(SA 19), and ethylzinc (t-butoxide) (SA20).

Examples 1-4 Comparative Examples A*-C* General High Throughput ParallelPolymerization Conditions

Polymerizations are conducted using a high throughput, parallelpolymerization reactor (PPR) available from Symyx technologies, Inc. andoperated substantially according to U.S. Pat. Nos. 6,248,540, 6,030,917,6,362,309, 6,306,658, and 6,316,663. Ethylene copolymerizations areconducted at 130° C. and 200 psi (1.4 MPa) with ethylene on demand using1.2 equivalents of cocatalyst 1 based on total catalyst used (1.1equivalents when MMAO is present). A series of polymerizations areconducted in a parallel pressure reactor (PPR) contained of 48individual reactor cells in a 6×8 array that are fitted with apre-weighed glass tube. The working volume in each reactor cell is 6000μL. Each cell is temperature and pressure controlled with stirringprovided by individual stirring paddles. The monomer gas and quench gasare plumbed directly into the PPR unit and controlled by automaticvalves. Liquid reagents are robotically added to each reactor cell bysyringes and the reservoir solvent is mixed alkanes. The order ofaddition is mixed alkanes solvent (4 ml), ethylene, 1-octene comonomer(1 ml), cocatalyst 1 or cocatalyst 1/MMAO mixture, shuttling agent, andcatalyst or catalyst mixture. When a mixture of cocatalyst 1 and MMAO ora mixture of two catalysts is used, the reagents are premixed in a smallvial immediately prior to addition to the reactor. When a reagent isomitted in an experiment, the above order of addition is otherwisemaintained. Polymerizations are conducted for approximately 1-2 minutes,until predetermined ethylene consumptions are reached. After quenchingwith CO, the reactors are cooled and the glass tubes are unloaded. Thetubes are transferred to a centrifuge/vacuum drying unit, and dried for12 hours at 60° C. The tubes containing dried polymer are weighed andthe difference between this weight and the tare weight gives the netyield of polymer. Results are contained in Table 1. In Table 1 andelsewhere in the application, comparative compounds are indicated by anasterisk (*).

Examples 1-4 demonstrate the synthesis of linear block copolymers by thepresent invention as evidenced by the formation of a very narrow MWD,essentially monomodal copolymer when DEZ is present and a bimodal, broadmolecular weight distribution product (a mixture of separately producedpolymers) in the absence of DEZ. Due to the fact that Catalyst (A1) isknown to incorporate more octene than Catalyst (B1), the differentblocks or segments of the resulting copolymers of the invention aredistinguishable based on branching or density.

TABLE 1 Cat. (A1) Cat (B1) Cocat MMAO shuttling Ex. (μmol) (μmol) (μmol)(μmol) agent (μmol) Yield (g) Mn Mw/Mn hexyls¹ A* 0.06 — 0.066 0.3 —0.1363 300502 3.32 — B* — 0.1 0.110 0.5 — 0.1581 36957 1.22 2.5 C* 0.060.1 0.176 0.8 — 0.2038 45526 5.30² 5.5 1 0.06 0.1 0.192 — DEZ (8.0)0.1974 28715 1.19 4.8 2 0.06 0.1 0.192 — DEZ (80.0) 0.1468 2161 1.1214.4 3 0.06 0.1 0.192 — TEA (8.0) 0.208 22675 1.71 4.6 4 0.06 0.1 0.192— TEA (80.0) 0.1879 3338 1.54 9.4 ¹C₆ or higher chain content per 1000carbons ²Bimodal molecular weight distribution

Further characterizing data for the polymers of Table 1 are determinedby reference to the figures. More specifically DSC and ATREF resultsshow the following:

The DSC curve for the polymer of example 1 shows a 115.7° C. meltingpoint (Tm) with a heat of fusion of 158.1 J/g. The corresponding CRYSTAFcurve shows the tallest peak at 34.5° C. with a peak area of 52.9percent. The difference between the DSC Tm and the Tcrystaf is 81.2° C.

The DSC curve for the polymer of example 2 shows a peak with a 109.7° C.melting point (Tm) with a heat of fusion of 214.0 J/g. The correspondingCRYSTAF curve shows the tallest peak at 46.2° C. with a peak area of57.0 percent. The difference between the DSC Tm and the Tcrystaf is63.5° C.

The DSC curve for the polymer of example 3 shows a peak with a 120.7° C.melting point (Tm) with a heat of fusion of 160.1 J/g. The correspondingCRYSTAF curve shows the tallest peak at 66.1° C. with a peak area of71.8 percent. The difference between the DSC Tm and the Tcrystaf is54.6° C.

The DSC curve for the polymer of example 4 shows a peak with a 104.5° C.melting point (Tm) with a heat of fusion of 170.7 J/g. The correspondingCRYSTAF curve shows the tallest peak at 30° C. with a peak area of 18.2percent. The difference between the DSC Tm and the Tcrystaf is 74.5° C.

The DSC curve for Comparative Example A* shows a 90.0° C. melting point(Tm) with a heat of fusion of 86.7 J/g. The corresponding CRYSTAF curveshows the tallest peak at 48.5° C. with a peak area of 29.4 percent.Both of these values are consistent with a resin that is low in density.The difference between the DSC Tm and the Tcrystaf is 41.8° C.

The DSC curve for Comparative Example B* shows a 129.8° C. melting point(Tm) with a heat of fusion of 237.0 J/g. The corresponding CRYSTAF curveshows the tallest peak at 82.4° C. with a peak area of 83.7 percent.Both of these values are consistent with a resin that is high indensity. The difference between the DSC Tm and the Tcrystaf is 47.4° C.

The DSC curve for Comparative Example C* shows a 125.3° C. melting point(Tm) with a heat of fusion of 143.0 J/g. The corresponding CRYSTAF curveshows the tallest peak at 81.8° C. with a peak area of 34.7 percent aswell as a lower crystalline peak at 52.4° C. The separation between thetwo peaks is consistent with the presence of a high crystalline and alow crystalline polymer. The difference between the DSC Tm and theTcrystaf is 43.5° C.

Examples 5-19 Comparatives D-F, Continuous Solution Polymerization,Catalyst A1/B2+DEZ

Continuous solution polymerizations are carried out in a computercontrolled autoclave reactor equipped with an internal stirrer. Purifiedmixed alkanes solvent (Isopar™ E available from ExxonMobil ChemicalCompany), ethylene at 2.70 lbs/hour (1.22 kg/hour), 1-octene, andhydrogen (where used) are supplied to a 3.8 L reactor equipped with ajacket for temperature control and an internal thermocouple. The solventfeed to the reactor is measured by a mass-flow controller. A variablespeed diaphragm pump controls the solvent flow rate and pressure to thereactor. At the discharge of the pump, a side stream is taken to provideflush flows for the catalyst and cocatalyst 1 injection lines and thereactor agitator. These flows are measured by Micro-Motion mass flowmeters and controlled by control valves or by the manual adjustment ofneedle valves. The remaining solvent is combined with 1-octene,ethylene, and hydrogen (where used) and fed to the reactor. A mass flowcontroller is used to deliver hydrogen to the reactor as needed. Thetemperature of the solvent/monomer solution is controlled by use of aheat exchanger before entering the reactor. This stream enters thebottom of the reactor. The catalyst component solutions are meteredusing pumps and mass flow meters and are combined with the catalystflush solvent and introduced into the bottom of the reactor. The reactoris run liquid-full at 500 psig (3.45 MPa) with vigorous stirring.Product is removed through exit lines at the top of the reactor. Allexit lines from the reactor are steam traced and insulated.Polymerization is stopped by the addition of a small amount of waterinto the exit line along with any stabilizers or other additives andpassing the mixture through a static mixer. The product stream is thenheated by passing through a heat exchanger before devolatilization. Thepolymer product is recovered by extrusion using a devolatilizingextruder and water cooled pelletizer. Process details and results arecontained in Table 2. Selected polymer properties are provided in Table3.

TABLE 2 Process details for preparation of exemplary polymers Cat Cat A1Cat B2 DEZ Cocat Cocat Poly C₈H₁₆ Solv. H₂ T A1² Flow B2³ Flow DEZ FlowConc. Flow [C₂H₄]/ Rate⁵ Ex. kg/hr kg/hr sccm¹ ° C. ppm kg/hr ppm kg/hrConc % kg/hr ppm kg/hr [DEZ]⁴ kg/hr Conv %⁶ Solids % Eff.⁷ D* 1.63 12.729.90 120 142.2 0.14 — — 0.19 0.32  820 0.17 536 1.81 88.8 11.2 95.2 E*″ 9.5 5.00 ″ — — 109 0.10 0.19 ″ 1743 0.40 485 1.47 89.9 11.3 126.8 F* ″11.3 251.6 ″ 71.7 0.06 30.8 0.06 — — ″ 0.11 — 1.55 88.5 10.3 257.7  5 ″″ — ″ ″ 0.14 30.8 0.13 0.17 0.43 ″ 0.26 419 1.64 89.6 11.1 118.3  6 ″ ″4.92 ″ ″ 0.10 30.4 0.08 0.17 0.32 ″ 0.18 570 1.65 89.3 11.1 172.7  7 ″ ″21.70 ″ ″ 0.07 30.8 0.06 0.17 0.25 ″ 0.13 718 1.60 89.2 10.6 244.1  8 ″″ 36.90 ″ ″ 0.06 ″ ″ ″ 0.10 ″ 0.12 1778 1.62 90.0 10.8 261.1  9 ″ ″78.43 ″ ″ ″ ″ ″ ″ 0.04 ″ ″ 4596 1.63 90.2 10.8 267.9 10 ″ ″ 0.00 12371.1 0.12 30.3 0.14 0.34 0.19 1743 0.08 415 1.67 90.31 11.1 131.1 11 ″ ″″ 120 71.1 0.16 ″ 0.17 0.80 0.15 1743 0.10 249 1.68 89.56 11.1 100.6 12″ ″ ″ 121 71.1 0.15 ″ 0.07 ″ 0.09 1743 0.07 396 1.70 90.02 11.3 137.0 13″ ″ ″ 122 71.1 0.12 ″ 0.06 ″ 0.05 1743 0.05 653 1.69 89.64 11.2 161.9 14″ ″ ″ 120 71.1 0.05 ″ 0.29 ″ 0.10 1743 0.10 395 1.41 89.42 9.3 114.1 152.45 ″ ″ ″ 71.1 0.14 ″ 0.17 ″ 0.14 1743 0.09 282 1.80 89.33 11.3 121.316 ″ ″ ″ 122 71.1 0.10 ″ 0.13 ″ 0.07 1743 0.07 485 1.78 90.11 11.2 159.717 ″ ″ ″ 121 71.1 0.10 ″ 0.14 ″ 0.08 1743 ″ 506 1.75 89.08 11.0 155.6 180.69 ″ ″ 121 71.1 ″ ″ 0.22 ″ 0.11 1743 0.10 331 1.25 89.93 8.8 90.2 190.32 ″ ″ 122 71.1 0.06 ″ ″ ″ 0.09 1743 0.08 367 1.16 90.74 8.4 106.0*Comparative, not an example of the invention ¹standard cm³/min²[N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafniumdimethyl³bis-(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)immino)zirconium dibenzyl ⁴molar ratio in reactor ⁵polymer production rate⁶percent ethylene conversion in reactor ⁷efficiency, kg polymer/g Mwhere g M = g Hf + g Zr

TABLE 3 Properties of exemplary polymers Heat of CRYSTAF Density Mw MnFusion T_(m) T_(c) T_(CRYSTAF) Tm − T_(CRYSTAF) Peak Area Ex. (g/cm³) I₂I₁₀ I₁₀/I₂ (g/mol) (g/mol) Mw/Mn (J/g) (° C.) (° C.) (° C.) (° C.)(percent) D* 0.8627 1.5 10.0 6.5 110,000 55,800 2.0 32 37 45 30 7 99 E*0.9378 7.0 39.0 5.6 65,000 33,300 2.0 183 124 113 79 45 95 F* 0.8895 0.912.5 13.4 137,300 9,980 13.8 90 125 111 78 47 20  5 0.8786 1.5 9.8 6.7104,600 53,200 2.0 55 120 101 48 72 60  6 0.8785 1.1 7.5 6.5 10960053300 2.1 55 115 94 44 71 63  7 0.8825 1.0 7.2 7.1 118,500 53,100 2.2 69121 103 49 72 29  8 0.8828 0.9 6.8 7.7 129,000 40,100 3.2 68 124 106 8043 13  9 0.8836 1.1 9.7 9.1 129600 28700 4.5 74 125 109 81 44 16 100.8784 1.2 7.5 6.5 113,100 58,200 1.9 54 116 92 41 75 52 11 0.8818 9.159.2 6.5 66,200 36,500 1.8 63 114 93 40 74 25 12 0.8700 2.1 13.2 6.4101,500 55,100 1.8 40 113 80 30 83 91 13 0.8718 0.7 4.4 6.5 132,10063,600 2.1 42 114 80 30 81 8 14 0.9116 2.6 15.6 6.0 81,900 43,600 1.9123 121 106 73 48 92 15 0.8719 6.0 41.6 6.9 79,900 40,100 2.0 33 114 9132 82 10 16 0.8758 0.5 3.4 7.1 148,500 74,900 2.0 43 117 96 48 69 65 170.8757 1.7 11.3 6.8 107,500 54,000 2.0 43 116 96 43 73 57 18 0.9192 4.124.9 6.1 72,000 37,900 1.9 136 120 106 70 50 94 19 0.9344 3.4 20.3 6.076,800 39,400 1.9 169 125 112 80 45 88

The resulting polymers are tested by DSC and ATREF as with previousexamples. Results are as follows:

The DSC curve for the polymer of example 5 shows a peak with a 119.6° C.melting point (Tm) with a heat of fusion of 60.0 J/g. The correspondingCRYSTAF curve shows the tallest peak at 47.6° C. with a peak area of59.5 percent. The delta between the DSC Tm and the Tcrystaf is 72.0° C.

The DSC curve for the polymer of example 6 shows a peak with a 115.2° C.melting point (Tm) with a heat of fusion of 60.4 J/g. The correspondingCRYSTAF curve shows the tallest peak at 44.2° C. with a peak area of62.7 percent. The delta between the DSC Tm and the Tcrystaf is 71.0° C.

The DSC curve for the polymer of example 7 shows a peak with a 121.3° C.melting point with a heat of fusion of 69.1 J/g. The correspondingCRYSTAF curve shows the tallest peak at 49.2° C. with a peak area of29.4 percent. The delta between the DSC Tm and the Tcrystaf is 72.1° C.

The DSC curve for the polymer of example 8 shows a peak with a 123.5° C.melting point (Tm) with a heat of fusion of 67.9 J/g. The correspondingCRYSTAF curve shows the tallest peak at 80.1° C. with a peak area of12.7 percent. The delta between the DSC Tm and the Tcrystaf is 43.4° C.

The DSC curve for the polymer of example 9 shows a peak with a 124.6° C.melting point (Tm) with a heat of fusion of 73.5 J/g. The correspondingCRYSTAF curve shows the tallest peak at 80.8° C. with a peak area of16.0 percent. The delta between the DSC Tm and the Tcrystaf is 43.8° C.

The DSC curve for the polymer of example 10 shows a peak with a 115.6°C. melting point (Tm) with a heat of fusion of 60.7 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 40.9° C. with apeak area of 52.4 percent. The delta between the DSC Tm and the Tcrystafis 74.7° C.

The DSC curve for the polymer of example 11 shows a peak with a 113.6°C. melting point (Tm) with a heat of fusion of 70.4 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 39.6° C. with apeak area of 25.2 percent. The delta between the DSC Tm and the Tcrystafis 74.1° C.

The DSC curve for the polymer of example 12 shows a peak with a 113.2°C. melting point (Tm) with a heat of fusion of 48.9 J/g. Thecorresponding CRYSTAF curve shows no peak equal to or above 30° C.(Tcrystaf for purposes of further calculation is therefore set at 30°C.). The delta between the DSC Tm and the Tcrystaf is 83.2° C.

The DSC curve for the polymer of example 13 shows a peak with a 114.4°C. melting point (Tm) with a heat of fusion of 49.4 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 33.8° C. with apeak area of 7.7 percent. The delta between the DSC Tm and the Tcrystafis 84.4° C.

The DSC for the polymer of example 14 shows a peak with a 120.8° C.melting point (Tm) with a heat of fusion of 127.9 J/g. The correspondingCRYSTAF curve shows the tallest peak at 72.9° C. with a peak area of92.2 percent. The delta between the DSC Tm and the Tcrystaf is 47.9° C.

The DSC curve for the polymer of example 15 shows a peak with a 114.3°C. melting point (Tm) with a heat of fusion of 36.2 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 32.3° C. with apeak area of 9.8 percent. The delta between the DSC Tm and the Tcrystafis 82.0° C.

The DSC curve for the polymer of example 16 shows a peak with a 116.6°C. melting point (Tm) with a heat of fusion of 44.9 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 48.0° C. with apeak area of 65.0 percent. The delta between the DSC Tm and the Tcrystafis 68.6° C.

The DSC curve for the polymer of example 17 shows a peak with a 116.0°C. melting point (Tm) with a heat of fusion of 47.0 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 43.1° C. with apeak area of 56.8 percent. The delta between the DSC Tm and the Tcrystafis 72.9° C.

The DSC curve for the polymer of example 18 shows a peak with a 120.5°C. melting point (Tm) with a heat of fusion of 141.8 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 70.0° C. with apeak area of 94.0 percent. The delta between the DSC Tm and the Tcrystafis 50.5° C.

The DSC curve for the polymer of example 19 shows a peak with a 124.8°C. melting point (Tm) with a heat of fusion of 174.8 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 79.9° C. with apeak area of 87.9 percent. The delta between the DSC Tm and the Tcrystafis 45.0° C.

The DSC curve for the polymer of Comparative Example D* shows a peakwith a 37.3° C. melting point (Tm) with a heat of fusion of 31.6 J/g.The corresponding CRYSTAF curve shows no peak equal to and above 30° C.Both of these values are consistent with a resin that is low in density.The delta between the DSC Tm and the Tcrystaf is 7.3° C.

The DSC curve for the polymer of Comparative Example E* shows a peakwith a 124.0° C. melting point (Tm) with a heat of fusion of 179.3 J/g.The corresponding CRYSTAF curve shows the tallest peak at 79.3° C. witha peak area of 94.6 percent. Both of these values are consistent with aresin that is high in density. The delta between the DSC Tm and theTcrystaf is 44.6° C.

The DSC curve for the polymer of Comparative Example F* shows a peakwith a 124.8° C. melting point (Tm) with a heat of fusion of 90.4 J/g.The corresponding CRYSTAF curve shows the tallest peak at 77.6° C. witha peak area of 19.5 percent. The separation between the two peaks isconsistent with the presence of both a high crystalline and a lowcrystalline polymer. The delta between the DSC Tm and the Tcrystaf is47.2° C.

Physical Property Testing

Polymer samples are evaluated for physical properties such as hightemperature resistance properties, as evidenced by TMA temperaturetesting, pellet blocking strength, high temperature recovery, hightemperature compression set and storage modulus ratio, G′(25°C.)/G′(100° C.). Several commercially available polymers are included inthe tests: Comparative Example G* is a substantially linearethylene/1-octene copolymer (AFFINITY®, available from The Dow ChemicalCompany), Comparative Example H* is an elastomeric, substantially linearethylene/1-octene copolymer (AFFINITY®EG8100, available from The DowChemical Company), Comparative Example I* is a substantially linearethylene/1-octene copolymer (AFFINITY®PL1840, available from The DowChemical Company), Comparative Example J* is a hydrogenatedstyrene/butadiene/styrene triblock copolymer (KRATON™ G1652, availablefrom KRATON Polymers), Comparative Example K* is a thermoplasticvulcanizate (TPV, a polyolefin blend containing dispersed therein acrosslinked elastomer). Results are presented in Table 4.

TABLE 4 High Temperature Mechanical Properties TMA-1 mm Pellet Blocking300% Strain Compression penetration Strength G′ (25° C.)/ Recovery (80°C.) Set (70° C.) Ex. (° C.) lb/ft² (kPa) G′ (100° C.) (percent)(percent) D* 51 — 9 Failed — E* 130 — 18 — — F* 70 141 (6.8)  9 Failed100  5 104 0 (0)  6 81 49  6 110 — 5 — 52  7 113 — 4 84 43  8 111 — 4Failed 41  9 97 — 4 — 66 10 108 — 5 81 55 11 100 — 8 — 68 12 88 — 8 — 7913 95 — 6 84 71 14 125 — 7 — — 15 96 — 5 — 58 16 113 — 4 — 42 17 108 0(0)  4 82 47 18 125 — 10 — — 19 133 — 9 — — G* 75 463 (22.2) 89 Failed100 H* 70 213 (10.2) 29 Failed 100 I* 111 — 11 — — J* 107 — 5 Failed 100K* 152 — 3 — 40

In Table 4, Comparative Example F* (which is a physical blend of the twopolymers resulting from simultaneous polymerizations using catalyst A1and B1) has a 1 mm penetration temperature of about 70° C., whileExamples 5-9 have a 1 mm penetration temperature of 100° C. or greater.Further, examples 10-19 all have a 1 mm penetration temperature ofgreater than 85° C., with most having 1 mm TMA temperature of greaterthan 90° C. or even greater than 100° C. This shows that the novelpolymers have better dimensional stability at higher temperaturescompared to a physical blend. Comparative Example J* (a commercial SEBS)has a good 1 mm TMA temperature of about 107° C., but it has very poor(high temperature 70° C.) compression set of about 100 percent and italso failed to recover (sample broke) during a high temperature (80° C.)300 percent strain recovery. Thus the exemplified polymers have a uniquecombination of properties unavailable even in some commerciallyavailable, high performance thermoplastic elastomers.

Similarly, Table 4 shows a low (good) storage modulus ratio, G′(25°C.)/G′(100° C.), for the inventive polymers of 6 or less, whereas aphysical blend (Comparative Example F*) has a storage modulus ratio of 9and a random ethylene/octene copolymer (Comparative Example G*) ofsimilar density has a storage modulus ratio an order of magnitudegreater (89). It is desirable that the storage modulus ratio of apolymer be as close to 1 as possible. Such polymers will be relativelyunaffected by temperature, and fabricated articles made from suchpolymers can be usefully employed over a broad temperature range. Thisfeature of low storage modulus ratio and temperature independence isparticularly useful in elastomer applications such as in pressuresensitive adhesive formulations.

The data in Table 4 also demonstrate that the polymers of the inventionpossess improved pellet blocking strength. In particular, Example 5 hasa pellet blocking strength of 0 MPa, meaning it is free flowing underthe conditions tested, compared to Comparatives F and G which showconsiderable blocking. Blocking strength is important since bulkshipment of polymers having large blocking strengths can result inproduct clumping or sticking together upon storage or shipping,resulting in poor handling properties.

High temperature (70° C.) compression set for the inventive polymers isgenerally good, meaning generally less than about 80 percent, preferablyless than about 70 percent and especially less than about 60 percent. Incontrast, Comparatives F, G, H and J all have a 70° C. compression setof 100 percent (the maximum possible value, indicating no recovery).Good high temperature compression set (low numerical values) isespecially needed for applications such as gaskets, window profiles,o-rings, and the like.

TABLE 5 Ambient Temperature Mechanical Properties Tensile 100% 300%Retractive Stress Abrasion: Notched Strain Strain Stress Com- Relax-Flex Tensile Tensile Elongation Tensile Elongation Volume Tear RecoveryRecovery at 150% pression ation Modulus Modulus Strength at Break¹Strength at Break Loss Strength 21° C. 21° C. Strain Set 21° C. at 50%Ex. (MPa) (MPa) (MPa)¹ (%) (MPa) (%) (mm³) (mJ) (percent) (percent)(kPa) (Percent) Strain² D* 12 5 — — 10 1074 — — 91 83 760 — — E* 895 589— 31 1029 — — — — — — — F* 57 46 — — 12 824 93 339 78 65 400 42 —  5 3024 14 951 16 1116 48 — 87 74 790 14 33  6 33 29 — — 14 938 — — — 75 86113 —  7 44 37 15 846 14 854 39 — 82 73 810 20 —  8 41 35 13 785 14 81045 461 82 74 760 22 —  9 43 38 — — 12 823 — — — — — 25 — 10 23 23 — — 14902 — — 86 75 860 12 — 11 30 26 — — 16 1090 — 976 89 66 510 14 30 12 2017 12 961 13 931 — 1247 91 75 700 17 — 13 16 14 — — 13 814 — 691 91 — —21 — 14 212 160 — — 29 857 — — — — — — — 15 18 14 12 1127  10 1573 —2074 89 83 770 14 — 16 23 20 — — 12 968 — — 88 83 1040  13 — 17 20 18 —— 13 1252 — 1274 13 83 920  4 — 18 323 239 — — 30 808 — — — — — — — 19706 483 — — 36 871 — — — — — — — G* 15 15 — — 17 1000 — 746 86 53 110 2750 H* 16 15 — — 15 829 — 569 87 60 380 23 — I* 210 147 — — 29 697 — — —— — — — J* — — — — 32 609 — — 93 96 1900  25 — K* — — — — — — — — — — —30 — Tested at 51 cm/minute measured at 38° C. for 12 hours

Table 5 shows results for mechanical properties for the new polymers aswell as for various comparison polymers at ambient temperatures. It maybe seen that the inventive polymers have very good abrasion resistancewhen tested according to ISO 4649, generally showing a volume loss ofless than about 90 mm³, preferably less than about 80 mm³, andespecially less than about 50 mm³. In this test, higher numbers indicatehigher volume loss and consequently lower abrasion resistance.

Tear strength as measured by tensile notched tear strength of theinventive polymers is generally 1000 mJ or higher, as shown in Table 5.Tear strength for the inventive polymers can be as high as 3000 mJ, oreven as high as 5000 mJ. Comparative polymers generally have tearstrengths no higher than 750 mJ.

Table 5 also shows that the polymers of the invention have betterretractive stress at 150 percent strain (demonstrated by higherretractive stress values) than some of the comparative samples.Comparative Examples F*, G* and H* have retractive stress value at 150percent strain of 400 kPa or less, while the inventive polymers haveretractive stress values at 150 percent strain of 500 kPa (Ex. 11) to ashigh as about 1100 kPa (Ex. 17). Polymers having higher than 150 percentretractive stress values would be quite useful for elastic applications,such as elastic fibers and fabrics, especially nonwoven fabrics. Otherapplications include diaper, hygiene, and medical garment waistbandapplications, such as tabs and elastic bands.

Table 5 also shows that stress relaxation (at 50 percent strain) is alsoimproved (less) for the inventive polymers as compared to, for example,Comparative Example G*. Lower stress relaxation means that the polymerretains its force better in applications such as diapers and othergarments where retention of elastic properties over long time periods atbody temperatures is desired.

Optical Testing

TABLE 6 Polymer Optical Properties Ex. Internal Haze (percent) Clarity(percent) 45° Gloss (percent) F* 84 22 49 G* 5 73 56  5 13 72 60  6 3369 53  7 28 57 59  8 20 65 62  9 61 38 49 10 15 73 67 11 13 69 67 12 875 72 13 7 74 69 14 59 15 62 15 11 74 66 16 39 70 65 17 29 73 66 18 6122 60 19 74 11 52 G* 5 73 56 H* 12 76 59 I* 20 75 59

The optical properties reported in Table 6 are based on compressionmolded films substantially lacking in orientation. Optical properties ofthe polymers may be varied over wide ranges, due to variation incrystallite size, resulting from variation in the quantity of chainshuttling agent employed in the polymerization.

Extractions of Multi-Block Copolymers

Extraction studies of the polymers of examples 5, 7 and ComparativeExample E* are conducted. In the experiments, the polymer sample isweighed into a glass fritted extraction thimble and fitted into aKumagawa type extractor. The extractor with sample is purged withnitrogen, and a 500 mL round bottom flask is charged with 350 mL ofdiethyl ether. The flask is then fitted to the extractor. The ether isheated while being stirred. Time is noted when the ether begins tocondense into the thimble, and the extraction is allowed to proceedunder nitrogen for 24 hours. At this time, heating is stopped and thesolution is allowed to cool. Any ether remaining in the extractor isreturned to the flask. The ether in the flask is evaporated under vacuumat ambient temperature, and the resulting solids are purged dry withnitrogen. Any residue is transferred to a weighed bottle usingsuccessive washes of hexane. The combined hexane washes are thenevaporated with another nitrogen purge, and the residue dried undervacuum overnight at 40° C. Any remaining ether in the extractor ispurged dry with nitrogen.

A second clean round bottom flask charged with 350 mL of hexane is thenconnected to the extractor. The hexane is heated to reflux with stirringand maintained at reflux for 24 hours after hexane is first noticedcondensing into the thimble. Heating is then stopped and the flask isallowed to cool. Any hexane remaining in the extractor is transferredback to the flask. The hexane is removed by evaporation under vacuum atambient temperature, and any residue remaining in the flask istransferred to a weighed bottle using successive hexane washes. Thehexane in the flask is evaporated by a nitrogen purge, and the residueis vacuum dried overnight at 40° C.

The polymer sample remaining in the thimble after the extractions istransferred from the thimble to a weighed bottle and vacuum driedovernight at 40° C. Results are contained in Table 7.

TABLE 7 ether ether C₈ hexane hexane C₈ residue wt. soluble soluble molesoluble soluble mole C₈ mole Sample (g) (g) (percent) percent¹ (g)(percent) percent¹ percent¹ Comp. 1.097 0.063 5.69 12.2 0.245 22.35 13.66.5 F* Ex. 5 1.006 0.041 4.08 — 0.040 3.98 14.2 11.6 Ex. 7 1.092 0.0171.59 13.3 0.012 1.10 11.7 9.9 ¹Determined by ¹³C NMR

ADDITIONAL POLYMER EXAMPLES 19A-F CONTINUOUS SOLUTION POLYMERIZATION,CATALYST A1/B2+DEZ

Continuous solution polymerizations are carried out in a computercontrolled well-mixed reactor. Purified mixed alkanes solvent (Isopar™ Eavailable from ExxonMobil Chemical Company), ethylene, 1-octene, andhydrogen (where used) are combined and fed to a 27 gallon reactor. Thefeeds to the reactor are measured by mass-flow controllers. Thetemperature of the feed stream is controlled by use of a glycol cooledheat exchanger before entering the reactor. The catalyst componentsolutions are metered using pumps and mass flow meters. The reactor isrun liquid-full at approximately 550 psig pressure. Upon exiting thereactor, water and additive are injected in the polymer solution. Thewater hydrolyzes the catalysts, and terminates the polymerizationreactions. The post reactor solution is then heated in preparation for atwo-stage devolatization. The solvent and unreacted monomers are removedduring the devolatization process. The polymer melt is pumped to a diefor underwater pellet cuffing.

Process details and results are contained in Table 7a. Selected polymerproperties are provided in Tables 7b-7c.

TABLE 7a Polymerization Conditions Cat Cat Cat Cat A1² A1 B2³ B2 DEZ DEZC₂H₄ C₈H₁₆ Solv. H₂ T Conc. Flow Conc. Flow Conc Flow Ex. lb/hr lb/hrlb/hr sccm¹ ° C. ppm lb/hr ppm lb/hr wt % lb/hr 19a 55.29 32.03 323.03101 120 600 0.25 200 0.42 3.0 0.70 19b 53.95 28.96 325.3 577 120 6000.25 200 0.55 3.0 0.24 19c 55.53 30.97 324.37 550 120 600 0.216 2000.609 3.0 0.69 19d 54.83 30.58 326.33 60 120 600 0.22 200 0.63 3.0 1.3919e 54.95 31.73 326.75 251 120 600 0.21 200 0.61 3.0 1.04 19f 50.4334.80 330.33 124 120 600 0.20 200 0.60 3.0 0.74 19g 50.25 33.08 325.61188 120 600 0.19 200 0.59 3.0 0.54 19h 50.15 34.87 318.17 58 120 6000.21 200 0.66 3.0 0.70 19i 55.02 34.02 323.59 53 120 600 0.44 200 0.743.0 1.72 19j 7.46 9.04 50.6 47 120 150 0.22 76.7 0.36 0.5 0.19 [Zn]⁴Cocat 1 Cocat 1 Cocat 2 Cocat 2 in Poly Conc. Flow Conc. Flow polymerRate⁵ Conv⁶ Polymer Ex. ppm lb/hr ppm lb/hr ppm lb/hr wt % wt % Eff.⁷19a 4500 0.65 525 0.33 248 83.94 88.0 17.28 297 19b 4500 0.63 525 0.1190 80.72 88.1 17.2 295 19c 4500 0.61 525 0.33 246 84.13 88.9 17.16 29319d 4500 0.66 525 0.66 491 82.56 88.1 17.07 280 19e 4500 0.64 525 0.49368 84.11 88.4 17.43 288 19f 4500 0.52 525 0.35 257 85.31 87.5 17.09 31919g 4500 0.51 525 0.16 194 83.72 87.5 17.34 333 19h 4500 0.52 525 0.70259 83.21 88.0 17.46 312 19i 4500 0.70 525 1.65 600 86.63 88.0 17.6 27519j — — — — — — — — — ¹standard cm³/min²[N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafniumdimethyl³bis-(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)immino)zirconium dimethyl ⁴ppm in final product calculated by mass balance⁵polymer production rate ⁶weight percent ethylene conversion in reactor⁷efficiency, kg polymer/g M where g M = g Hf + g Z

TABLE 7b Polymer Physical properties Heat of Tm − CRYSTAF PolymerDensity Mw Mn Fusion Tm TCRYSTAF TCRYSTAF Peak Area Ex. No. (g/cc) I₂I₁₀ I₁₀/I₂ (g/mol) (g/mol) Mw/Mn (J/g) (° C.) Tc (° C.) (° C.) (° C.)(wt %) 19g 0.8649 0.9 6.4 7.1 135000 64800 2.1 26 120 92 30 90 90 19h0.8654 1.0 7.0 7.1 131600 66900 2.0 26 118 88 — — —

TABLE 7c Average Block Index For exemplary polymers¹ Example Zn/C₂ ²Average BI Polymer F 0 0 Polymer 8 0.56 0.59 Polymer 19a 1.3 0.62Polymer 5 2.4 0.52 Polymer 19b 0.56 0.54 Polymer 19h 3.15 0.59¹Additional information regarding the calculation of the block indicesfor various polymers is disclosed in U.S. Pat. No. 7,608,668, entitled“Ethylene/α-Olefin Block Interpolymers”, filed on Mar. 15, 2006, in thename of Colin L. P. Shan, Lonnie Hazlitt, et. al. and assigned to DowGlobal Technologies Inc., the disclose of which is incorporated byreference herein in its entirety. ²Zn/C₂ * 1000 = (Zn feed flow * Znconcentration/1000000/Mw of Zn)/(Total Ethylene feed flow * (1 −fractional ethylene conversion rate)/Mw of Ethylene) * 1000. Please notethat “Zn” in “Zn/C₂ * 1000” refers to the amount of zinc in diethyl zinc(“DEZ”) used in the polymerization process, and “C2” refers to theamount of ethylene used in the polymerization process.

Examples 20-22 Ethylene/α-Olefin Interpolymers

Continuous solution polymerizations were carried out in a computercontrolled well-mixed reactor. Purified mixed alkanes solvent (ISOPAR™ Eavailable from ExxonMobil Chemical Company), ethylene, 1-octene, andhydrogen (where used) were combined and fed to a 102 L reactor. Thefeeds to the reactor were measured by mass-flow controllers. Thetemperature of the feed stream was controlled by use of a glycol cooledheat exchanger before entering the reactor. The catalyst componentsolutions were metered using pumps and mass flow meters. The reactor wasrun liquid-full at approximately 550 psig pressure. Upon exiting thereactor, water and additive were injected in the polymer solution. Thewater hydrolyzed the catalysts, and terminated the polymerizationreactions. The post reactor solution was then heated in preparation fora two-stage devolatilization. The solvent and unreacted monomers wereremoved during the devolatilization process. The polymer melt was pumpedto a die for underwater pellet cutting. Process details and results arecontained in Table 8.

Examples 23-26 Ethylene/α-Olefin Interpolymers

Continuous solution polymerizations were carried out in a computercontrolled well-mixed reactor equipped with an internal stirrer.Purified mixed alkanes solvent (ISOPAR™ E available from ExxonMobilChemical Company), ethylene, 1-octene, and hydrogen (where used) weresupplied to a 5.0 L reactor equipped with a jacket for temperaturecontrol and an internal thermocouple. The solvent fed to the reactor wasmeasured by a mass-flow controller. A variable speed diaphragm pumpcontrolled the solvent flow rate and pressure to the reactor. At thedischarge of the pump, a side stream was taken to provide flush flowsfor the catalyst and cocatalyst 1 injection lines and the reactoragitator. These flows were measured by Micro-Motion mass flow meters andcontrolled by control valves or by the manual adjustment of needlevalves. The remaining solvent was combined with 1-octene, ethylene, andhydrogen (where used) and fed to the reactor. A mass flow controller wasused to deliver hydrogen to the reactor as needed. The temperature ofthe solvent/monomer solution was controlled by using a heat exchangerbefore entering the reactor. This stream entered the bottom of thereactor. The catalyst component solutions were metered using pumps andmass flow meters and were combined with the catalyst flush solvent andintroduced into the bottom of the reactor. The reactor was runliquid-full at 406-psig (2.8 MPa) with vigorous stirring. Product wasremoved through exit lines at the top of the reactor. All exit linesfrom the reactor were steam traced and insulated. Polymerization wasstopped by the addition of a small amount of water into the exit linealong with any stabilizers or other additives and passing the mixturethrough a static mixer. The product stream was then heated up throughheat exchangers, and passed through two devolatizers in series before itwas water cooled. Process details and results are contained in Table 8.

Testing of Examples 20-26

Standard CRYSTAF Method. Branching distributions were determined bycrystallization analysis fractionation (CRYSTAF) using a CRYSTAF 200unit commercially available from PolymerChar, Valencia, Spain. Thesamples were dissolved in 1,2,4-trichlorobenzene at 160° C. (0.66 mg/mL)for 1 hour and stabilized at 95° C. for 45 minutes. The samplingtemperatures ranged from 95 to 30° C. at a cooling rate of 0.2° C./min.An infrared detector was used to measure the polymer solutionconcentrations. The cumulative soluble concentration was measured as thepolymer crystallized while the temperature was decreased. The analyticalderivative of the cumulative profile reflected the short chain branchingdistribution of the polymer.

The CRYSTAF peak temperature and area were identified by the peakanalysis module included in the CRYSTAF Software (Version 2001.b,PolymerChar, Valencia, Spain). The CRYSTAF peak finding routineidentified a peak temperature as a maximum in the dW/dT curve and thearea between the largest positive inflections on either side of theidentified peak in the derivative curve. To calculate the CRYSTAF curve,the preferred processing parameters were with a temperature limit of 70°C. and with smoothing parameters above the temperature limit of 0.1, andbelow the temperature limit of 0.3. The CRYSTAF peak temperature and thepeak area of each example are listed in Table 9 below.

DSC Standard Method for Polymers. Differential Scanning Calorimetryresults were determined using a TAI model Q1000 DSC equipped with an RCScooling accessory and an autosampler. A nitrogen purge gas flow of 50ml/min was used. The sample was pressed into a thin film and melted inthe press at about 175° C. and then air-cooled to room temperature (25°C.). The sample (˜3-10 mg) was then cut into a 6 mm diameter disk,accurately weighed, placed in a light aluminum pan (˜50 mg), and thencrimped shut. The thermal behavior of the sample was investigated withthe following temperature profile. The sample was rapidly heated to 180°C. and held isothermal for 3 minutes in order to remove any previousthermal history. The sample was then cooled to −40° C. at 10° C./mincooling rate and held at −40° C. for 3 minutes. The sample was thenheated to 150° C. at 10° C./minute heating rate. The cooling and secondheating curves were recorded. The melting peak (T_(m)) and cooling peak(T_(c)) were determined.

Where a minor melting or cooling peak was observed, the peak was notedas T_(m2) or T_(c2). The heat of fusion, T_(m) and T_(c) of each exampleare listed in Table 9 below.

GPC Method. The gel permeation chromatographic system consisted ofeither a Polymer Laboratories Model PL-210 or a Polymer LaboratoriesModel PL-220 instrument. The column and carousel compartments wereoperated at 140° C. Three Polymer Laboratories 10-micron Mixed-B columnswere used. The solvent was 1,2,4-trichlorobenzene. The samples wereprepared at a concentration of 0.1 grams of polymer in 50 milliliters ofsolvent containing 200 ppm of butylated hydroxytoluene (BHT). Sampleswere prepared by agitating lightly for 2 hours at 160° C. The injectionvolume used was 100 microliters and the flow rate was 1.0 ml/minute.

Calibration of the GPC column set was performed with 21 narrow molecularweight distribution polystyrene standards with molecular weights rangingfrom 580 to 8,400,000, daltons arranged in 6 “cocktail” mixtures with atleast a decade of separation between individual molecular weights. Thestandards were purchased from Polymer Laboratories (Shropshire, UK). Thepolystyrene standards were prepared at 0.025 grams in 50 milliliters ofsolvent for molecular weights equal to or greater than 1,000,000, and0.05 grams in 50 milliliters of solvent for molecular weights less than1,000,000. The polystyrene standards were dissolved at 80° C. withgentle agitation for 30 minutes. The narrow standards mixtures were runfirst and in order of decreasing highest molecular weight component tominimize degradation. The polystyrene standard peak molecular weightswere converted to polyethylene molecular weights using the followingequation (as described in Williams and Ward, J. Polym. Sci., Polym.Let., 6,621 (1968)): M_(polyethylene)=0.431 (M_(polystyrene)).Polyethylene equivalent molecular weight calculations are performedusing Viscotek TriSEC software Version 3.0. In Table 9, the weightaverage molecular weight M_(w), the number average molecular weightM_(n), and their ratio M_(w)/M_(n) are reported.

Density. Samples for density measurement were prepared according to ASTMD 1928. Density measurements were made within one hour of samplepressing using ASTM D792, Method B, which is incorporated herein byreference. The density of each example is listed in Table 9 below.

Melt Index. Melt index, I₂, was measured in accordance with ASTM D 1238,Condition 190° C./2.16 kg. Melt index, I₁₀, is also measured inaccordance with ASTM D 1238, Condition 190° C./10 kg. The I₂, I₁₀ andI₁₀/I₂ ratio of each example are listed in Table 9 below.

TABLE 8 Process Conditions and Results for Examples 20-26. Cat A1 Cat B2DEZ C₂H₄ C₈H₁₆ Solv. H₂ Temp Cat A1² Flow Cat B2³ Flow DEZ Flow Examplekg/hr kg/hr kg/hr sccm¹ ° C. ppm kg/hr ppm kg/hr Conc. % kg/hr 20⁸ 25.014.5 150.2 4122 120 410 0.26 200 0.12 0.0 0.00 21⁸ 25.0 14.2 150.4 267120 410 0.28 200 0.10 3.0 0.47 22⁸ 25.0 15.8 149.3 55 120 378 0.33 1000.21 3.0 0.79 23⁹ 2.5 4.1 22.0 2 120 150 0.097 76.6 0.036 0.532 0.2 24⁹2.8 4.1 21.6 2 120 150 0.095 76.6 0.041 0.532 0.2 25¹⁰ 2.5 4.5 21.0 345121 150 0.092 76.6 0.049 1.0 0.3 26¹⁰ 2.7 3.6 21.0 200 121 150 0.09476.6 0.049 1.0 0.3 Cocat 1 Cocat 1 Cocat 2 Cocat 2 Zn⁴ Poly Conc. FlowConc. Flow in polymer Rate⁵ Conv. Example ppm kg/hr ppm kg/hr ppm kg/hr%⁶ Solids % Eff.⁷ 20⁸ 4500 0.30 524 0.29 0 38.8 88.3 17.5 293 21⁸ 45830.29 524 0.22 370 38.4 88.4 17.4 281 22⁸ 4500 0.32 260 0.75 588 40.388.3 18.0 278 23⁹ 1008 159 0 0 244 4.0 89.0 14.0 231 24⁹ 1008 163 0 0250 4.0 90.0 14.0 230 25¹⁰ 1008 0.17 0 0 732 4.1 90.0 16.4 233 26¹⁰ 10080.16 0 0 750 4.0 90.0 16.0 232 ¹standard cm³/min²[N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafniumdimethyl³bis-(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)immino)zirconium dibenzyl ⁴ppm in final product calculated by mass balance⁵polymer production rate ⁶weight percent ethylene conversion in reactor⁷efficiency, kg polymer/g M where g M = g Hf + g Z ⁸Additive package:1000 ppm Irgafos 168, 250 ppm Irganox 1076, 200 ppm Irganox 1010, and100 ppm Chimmasorb 2020. ⁹Additive package: 1000 ppm Irgafos 168, 250ppm Irganox 1076, 200 ppm Irganox 1010, and 60 ppm Chimmasorb 2020.¹⁰Additive package: 1200 ppm Irganox 1010.

TABLE 9 Various Physical Properties of Examples 20-24 and OtherComparative Polymers Heat of CRYSTAF Density M_(w) M_(n) FusionT_(m)/T_(m2) T_(c)/T_(c2) T_(CRYSTAF) T_(m) − T_(CRYSTAF) Peak AreaExample (g/cm³) I₂ ⁷ I₁₀ ⁷ I₁₀/I₂ ⁷ (g/mol) (g/mol) M_(w)/M_(n) (J/g) (°C.) (° C.) (° C.) (° C.) (percent) 20 0.8741 1.0 13.0 13.0 148,30013,100 11.3 50 122 107 77 46 14 21 0.8750 4.9 33.5 6.8 81,800 41,700 2.049 121 97 36 84 12 22 0.8774 11.2 75.2 6.7 66,400 33,700 2.0 49 119 9940 79 13 23 0.8667 1.2 8.2 6.8 126,200 57,100 2.2 22 116 86 30 86  6 240.8771 0.9 6.2 6.9 124,000 60,200 2.1 58 117 97 40 77 47 ENGAGE ® 0.87101.1 8.2 7.4 114,500 56,500 2.0 48 59 45 NM NA NM 8100¹ ENGAGE ® 0.87124.9 37.1 7.6 79,900 39,200 2.0 52 64 46 NM NA NM 8200² LPE³ 0.8707 10.487.4 8.4 67,200 31,400 2.1 52  64/49 46 NM NA NM [70% LPE & 0.8936 11.484.0 7.4 65,300 25,500 2.6 98 127/66 114/49 NM NA NM 30% 12450N⁴]⁸KRATON ® 0.9076 0.24 2.57 10.7 37,400 34,400 1.1 17 14 3 NM NA NM 1652⁵VECTOR ® 0.9417 3.1 23.7 7.6 53,500 49,300 1.1 ND ND ND NM NA NM 4211⁶¹ENGAGE ® 8100 is a polyolefin elastomer obtained from The Dow ChemicalCo., Midland, MI. ²ENGAGE ® 8200 is a polyolefin elastomer obtained fromThe Dow Chemical Co., Midland, MI. ³LPE is a homogeneously branchedsubstantially linear polyethylene as described by Lai et al. in U.S.Pat. Nos. 5,272,236, 5,278,272, 5,665,800 and 5,783,638. ⁴12540N is highdensity polyethylene from The Dow Chemical Company, Midland, MI.⁵KRATON ® 1652 is a SEBS copolymer obtained from Kraton Polymers,Houston, TX. ⁶VECTOR ® 4211 is a SIS from Dexco Polymers, Houston, TX.⁷Measured at 190° C. ⁸This sample was produced by blending the twocomponents in a Haake mixer bowl. NM: Not measured NA: Not applicableND: Not detected

Tensile Mechanical Properties. Stress-strain behavior in uniaxialtension was measured using ASTM D 1708 microtensile specimens. Sampleswere stretched with an Instron at 500% min⁻¹ at 21° C. The tensilestrength and elongation at break of each example were reported from anaverage of 5 specimens and are listed in Table 10 below.

Thermal Mechanical Analysis (TMA). The penetration temperature wasconducted on 30 mm diameter×3.3 mm thick, compression molded discs,formed at 180° C. and 10 MPa molding pressure for 5 minutes and then airquenched. The instrument used was a Perkin-Elmer TMA 7. In the test, aprobe with 1.5 mm radius tip (P/N N519-0416) was applied to the surfaceof the sample disc with 1N force. The temperature was raised at 5°C./minute from 25° C. The probe penetration distance was measured as afunction of temperature. The experiment ended when the probe hadpenetrated 1 mm into the sample. The 1 mm penetration temperature ofeach example is listed in Table 10 below.

TABLE 10 The Tensile and Thermal Mechanical Properties of Examples20-26, ENGAGE ® 8100, ENGAGE ® 8200, KRATON ® 1652, LPE³, 12450N andVECTOR ® 4211. TMA-1 mm Tensile Strength Elongation Example penetration(° C.) (MPa) at Break (%) 20 50 8 1,349 21 100 13 1,459 22 101 9 1,62323 96 12 1,355 24 112 22 955 25 41 NM NM 26 54 NM NM ENGAGE ® 8100¹ 7015 829 ENGAGE ® 8200² 56 6 563 LPE³ 53 12 1,277 [70% LPE & 30% 62 151,097 12450N⁴]⁷ KRATON ® 1652⁵ 107 32 609 VECTOR ® 4211⁶ 85 15 1209¹ENGAGE ® 8100 is a polyolefin elastomer obtained from The Dow ChemicalCo., Midland, MI. ²ENGAGE ® 8200 is a polyolefin elastomer obtained fromThe Dow Chemical Co., Midland, MI. ³LPE is a homogeneously branchedsubstantially linear polyethylene as described by Lai et al. in U.S.Pat. Nos. 5,272,236, 5,278,272, 5,665,800 and 5,783,638. ⁴12540N is highdensity polyethylene from The Dow Chemical Company, Midland, MI.⁵KRATON ® 1652 is a SEBS copolymer obtained from Kraton Polymers,Houston, TX. ⁶VECTOR ® 4211 is a SIS from Dexco Polymers, Houston, TX.⁷This sample was produced by blending the two components in a Haakemixer bowl.

ETHYLENE/α-OLEFIN INTERPOLYMERS EXAMPLES 27-31, 31a and 31b

Examples 27, 29, and 31b were prepared using a process similar to theone as described herein for Example 22.

Process Details for Examples 28, 30, 31 and 31a

Continuous solution polymerizations are carried out in a computercontrolled well-mixed reactor. Purified mixed alkanes solvent (ISOPAR™ Eavailable from ExxonMobil Chemical Company), ethylene, 1-octene, andhydrogen (where used) are combined and fed to a 39 gallon reactor. Thefeeds to the reactor are measured by mass-flow controllers. Thetemperature of the feed stream is controlled by use of a glycol cooledheat exchanger before entering the reactor. The catalyst componentsolutions are metered using pumps and mass flow meters. The reactor isrun liquid-full at approximately 725 psig pressure. Upon exiting thereactor, water and additive are injected in the polymer solution. Thewater hydrolyzes the catalysts, and terminates the polymerizationreactions. The post reactor solution is then heated in preparation for atwo-stage devolatization. The solvent and unreacted monomers are removedduring the devolatization process. The polymer melt is pumped to a diefor underwater pellet cutting. Process details for interpolymers ofExamples 27-31, 31a, and 31b and results are contained in Table 10a.Selected polymer properties are provided in Tables 10b and 10c.

TABLE 10a Process Conditions and Results for Examples 27-31, 31a-31d.Cat Cat Inter- Cat A1 Cat B2 DEZ DEZ polymer C₂H₄ C₈H₁₆ Solv. H₂ TempA1² Flow B2³ Flow Conc. Flow Example kg/hr kg/hr kg/hr sccm¹ ° C. ppmkg/hr ppm kg/hr ppm kg/hr 27⁸ 22.8 45.4 179.7 217 120 400 0.27 100 0.0873.0 0.25 28⁸ 55.4 30.2 426.7 716 120 526 0.63 299 0.23 4.8 0.43 29⁸ 28.843.4 200.6 115 126 378 0.34 109 0.46 3.0 0.33 30⁸ 50.4 36.0 430.2 2499120 543 0.60 299 0.12 5.0 0.41 31⁸ 54.9 32.7 420.7 547 120 526 0.72 2990.24 4.8 0.86 31⁸ 55.4 33.2 426.7 600 120 555 0.94 299 0.38 5.0 1.2331b⁸ 25.0 47.9 181.9 60 120 500 0.29 200 0.18 5.0 0.66 31c⁹ 52.2 30.3438.8 132 120 654 0.85 148 0.16 5.0 1.3 31d⁹ 48.6 43.4 393.1 520 115 2351.65 148 0.25 5.0 1.0 Inter- Cocat 1 Cocat 1 Cocat 2 Cocat 2 Zn in Polypolymer Conc. Flow Conc. Flow polymer Rate⁵ Conv. Solids Example ppmkg/hr ppm kg/hr ppm kh/hr %⁶ % Eff.⁷ 27⁸ 4500 0.23 524 0.094 194 38.187.5 17.4 331 28⁸ 4786 0.79 348 0.49 228 89.7 88.6 18.5 224 29⁸ 45000.45 260 0.31 250 39.2 89.9 16.2 220 30⁸ 5140 0.62 1377 0.12 238 85.587.6 17.7 237 31⁸ 4786 0.88 348 0.98 448 92.0 88.7 19.2 203 31⁸ 49251.22 1377 0.37 670 91.7 88.5 18.9 143 31b⁸ 6000 0.36 518 0.66 821 40.488.5 18.1 221 31c⁹ 5400 0.90 399 1.35 762 85.5 91.4 17.3 147 31d⁹ 55210.67 860 0.49 559 90.9 88.4 20.5 213 ¹standard cm³/min²[N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafniumdimethyl³bis-(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)immino)zirconium dibenzyl ⁴ppm in final product calculated by mass balance⁵polymer production rate ⁶weight percent ethylene conversion in reactor⁷efficiency, kg polymer/g M where g M = g Hf + g Z ⁸Additive package:1000 ppm Irgafos 168, 250 ppm Irganox 1076, 200 ppm Irganox 1010, and100 ppm Chimmasorb 2020. ⁹Additive package: 1000 ppm Irgafos 168, 250ppm Irganox 1076, 200 ppm Irganox 1010, and 80 ppm Chimmasorb 2020.

TABLE 10b Various Physical Properties of Examples 27-31, 31a-31d. Heatof Tm − Crystaf Density Mw Mn Fusion Tcrystaf Tcrystaf Peak Example(g/cc) I2¹ I10¹ I10/I2¹ (g/mol) (g/mol) Mw/Mn (J/g) T_(m) (° C.) T_(c)(° C.) (° C.) (° C.) Area 27 0.8649 0.9 6.4 7.1 135,000 64,800 2.1 26120 92 30 90 90 28 0.8769 1.0 6.9 6.9 127,200 58,200 2.2 57 120 97 41 7913 29 0.8929 1.0 7.0 6.9 107,500 52,500 2.0 89 120 101 63 57 83 300.8665 5.0 36.0 7.3 93,200 41,100 2.3 30 122 97 30 92 93 31 0.8775 5.034.5 6.9 84,300 42,400 2.0 54 119 95 41 78 29 31a 0.8783 14.6 96.9 6.663,600 32,100 2.0 51 116 94 37 80 13 31b 0.8780 32.9 215.6 6.6 52,20028,000 1.9 54 119 97 39 80  6 31c 0.8699 15.2 95.6 6.3 60,100 30,900 1.944 108/40 74 NM NM NM 31d 0.8701 13.9 100.2 7.2 68,400 34,800 2.0 31 11798 NM NM NM ¹Measured at 190° C.

TABLE 10c The Tensile and Thermal Mechanical Properties of Examples27-31, 31a-31d. TMA, 1 mm Tensile Elongation penetration Strength atBreak Example (° C.) (MPa) (%) 27 83 12 1,305 28 107 16 1,002 29 119 261,063 30 68 8 1,646 31 100 13 1,313 31a 95 9 1,520 31b 88 4 1,507 31c 518 1,420 31d NM 4 2,201

General Procedure for the Preparation of Adhesive Formulations

An 18 mm 30:1 L/D twin screw Leistritz extruder (Micro 18 GL, obtainedfrom American Leistritz Extruder Corporation, Somerville, N.J.) with aHaake computer control program was used to formulate the adhesives. Thescrew design was a 30:1 L/D corotating twin screw with two sections of aseries of kneading blocks for shear mixing preceeded by forwardingsections and followed by a pressuring section to force the blend througha strand die. The nonfeed throat zones were set at 80, 120, 145, 160,and 160° C. The die was heated to 160° C. The pressure sensitiveadhesive (PSA) formulations were made using calibrated K-TRON feederswith one for the tackifier and another for the polymer. The oil wasinjected at Zone 2 using a calibrated positive displacement pump. Theextruder screw was turned at a drive speed from 150 to 200 rpm dependingon the blend to effect maximum blending. The extrudate was purged about3 minutes prior to collection in a wax paper lined pan. The componentsof the hot melt adhesive (HMA) blends were dry blended and then fed as asingle component through one K-TRON feeder. The blended feed was proddedcontinuously into the extruder using a high density polyethylene (HDPE)polyrod. As before, the extrudate was purged about 3 minutes prior tocollection in the pan.

Although these particular samples were made on a micro twin screwextruder, other mixing methods could have been used as well. Theseinclude the use of a Sigma blade mixer or a Haake bowl mixer. A generalprocedure would be to preheat the mixer to about 163° C. (325° F.). Insome cases a nitrogen blanket may be used on the mixer. The desiredamount of tackifier and stabilizer are then added and mixed until meltedcompletely. The polymer is then added while mixing until all of thepolymer is in the mixer. The mixer would then be covered and thecontents mixed until the formulation was smooth and free of lumps. Theoil is then slowly added and mixed for about 15 minutes until totallysmooth. The contents are then discharged into a suitable release linedcontainer. The total batch time should not exceed two hours. This is ageneral description, and variations may occur depending on thecomponents of the formulation.

TABLE 11 The Formulations and Viscosities of Adhesive Examples 32-69 andComparatives L-Z and AA-AE. Brookfield Kaydol Viscosity Adhesive PolymerTackifier Oil⁴ 177° C. Sample Polymer Tackifer wt % wt % wt % (cP) Ex.32 23 WINGTACK ® 95¹ 25.5%   54% 20% 69,285 Ex. 33 24 WINGTACK ® 9525.5%   54% 20% 24,745 Comp. L ENGAGE ® 8100⁵ WINGTACK ® 95 25.5%   54%20% 58,687 Ex. 34 20 WINGTACK ® 95 25.5%   54% 20% 134,221 Ex. 35 21WINGTACK ® 95 25.5%   54% 20% 33,593 Comp. M ENGAGE ® 8200⁶ WINGTACK ®95 25.5%   54% 20% 18,266 Ex. 36 22 WINGTACK ® 95 25.5%   54% 20% 10,958Comp. N LPE⁷ WINGTACK ® 95 25.5%   54% 20% 6,563 Comp. O 70% LPE &WINGTACK ® 95 25.5%   54% 20% 10,158 30% 12450N⁸ Comp. P KRATON ® 1652⁹WINGTACK ® 95 25.5%   54% 20% 8,488 Comp. Q VECTOR ® 4211¹⁰ WINGTACK ®95 25.5%   54% 20% 5,239 Ex. 37 22 EASTOTAC ® 22.5%   53% 25% 8,248H142R² Comp. R LPE⁷ EASTOTAC ® 22.5%   53% 25% 7,990 H142R Comp. S 70%LPE & EASTOTAC ® 22.5%   53% 25% 12,537 30% 12450N⁸ H142R Ex. 38 22EASTOTAC ® 19.5%   50% 30% 1,182 H142R Comp. T LPE⁷ EASTOTAC ® 19.5%  50% 30% 2,779 H142R Comp. U 70% LPE & EASTOTAC ® 19.5%   50% 30% 3,20430% 12450N⁸ H142R Ex. 39 22 EASTOTAC ® 14.5%   55% 30% 1,896 H142R Comp.V LPE⁷ EASTOTAC ® 14.5%   55% 30% 1,005 H142R Comp. W 70% LPE &EASTOTAC ® 14.5%   55% 30% 3,569 30% 12450N⁸ H142R Ex. 40 23 EASTOTAC ®15% 45% 40% 5,309 H142R Ex. 42 23 EASTOTAC ® 20% 40% 40% 15,376 H142REx. 43 23 EASTOTAC ® 10% 60% 30% 3,611 H142R Ex. 44 23 EASTOTAC ® 26%54% 20% 189,959 H142R Ex. 45 23 EASTOTAC ® 40% 40% 20% >300,000 H142REx. 46 23 EASTOTAC ® 10% 50% 40% 535 H142R Ex. 47 24 EASTOTAC ® 40% 40%20% >300,000 H142R Ex. 48 24 EASTOTAC ® 20% 40% 40% 35,043 H142R Comp. XKRATON ® G- EASTOTAC ® 20% 40% 40% 951 1652 H142R Comp. Y ENGAGE ® 8100EASTOTAC ® 20% 40% 40% 34,853 H142R Ex. 49 23 WINGTACK ® 95 20% 40% 40%16,047 Ex. 50 23 EASTOTAC ® 26% 47% 27% 106,102 H142R Ex. 51 23EASTOTAC ® 20% 50% 30% 30,054 H142R Ex. 52 23 EASTOTAC ® 30% 40% 30%172,151 H142R Ex. 53 23 EASTOTAC ® 10% 70% 20% 943 H142R Ex. 54 23EASTOTAC ® 20% 70% 10% 36,592 H142R Ex. 55 23 EASTOTAC ® 30% 70%0% >300,000 H142R Ex. 56 23 EASTOTAC ® 45% 55%  0% >300,000 H142R Ex. 5723 EASTOTAC ® 60% 40%  0% >300,000 H142R Ex. 58 23 EASTOTAC ® 60%  0%40% >300,000 H142R Ex. 59 23 EASTOTAC ® 40%  0% 60{circumflex over( )} >300,000 H142R Comp. Z KRATON ® G- WINGTACK ® 95 30% 54.50%   15%5,829 1652 Comp. AA ENGAGE ® 8100 WINGTACK ® 95 30% 54.50%   15% 234,012Comp. AB 62% ENGAGE ® WINGTACK ® 95 30% 54.50%   15% 118,100 8100 38%AFFINITY ® PL1880 Ex. 60  7 WINGTACK ® 95 30% 54.50%   15% 243,073 Ex.61  5 WINGTACK ® 95 30% 54.50%   15% 141,845 Ex. 62  8 WINGTACK ® 95 30%54.50%   15% >300,000 Ex. 63 13 WINGTACK ® 95 30% 54.50%   15% 160,903Ex. 64 16 WINGTACK ® 95 30% 54.50%   15% 223,389 Comp. AC KRATON ® G-ESCOREZ ™ 5400³ 30% 29.50%   40% 3.641 1652 Comp. AD ENGAGE ® 8100ESCOREZ ™ 5400 30% 29.50%   40% 89,981 Comp. AE 62% ENGAGE ® ESCOREZ ™5400 30% 29.50%   40% 66,267 8100/ 38% AFFINITY ® PL1880 Ex. 65  8ESCOREZ ™ 5400 30% 29.50%   40% 133,097 Ex. 66  5 ESCOREZ ™ 5400 30%29.50%   40% 105,602 Ex. 67  7 ESCOREZ ™ 5400 30% 29.50%   40% 109,820Ex. 68 13 ESCOREZ ™ 5400 30% 29.50%   40% 182,461 Ex. 69 16 ESCOREZ ™5400 30% 29.50%   40% 177,774 ¹WINGTACK ® 95 is a tackifier fromGoodYear Chemical, Beaumont, TX. ²EASTOTAC ® H142R is a tackifier fromEastman Company, Kingsport, Tennessee. ³ESCOREZ ™ 5400 is a tackifierfrom ExxonMobil Chemical Company, Houston, TX. ⁴Kaydol Oil is a mineraloil from AMCO Chemical, Oakland, CA. ⁵ENGAGE ® 8100 is a polyolefinelastomer obtained from The Dow Chemical Co., Midland, MI. ⁶ENGAGE ®8200 is a polyolefin elastomer obtained from The Dow Chemical Co.,Midland, MI. ⁷LPE is a homogeneously branched substantially linearpolyethylene as described by Lai et al. in U.S. Pat. Nos. 5,272,236,5,278,272, 5,665,800 and 5,783,638. ⁸12540N is high density polyethylenefrom The Dow Chemical Company, Midland, MI. ⁹KRATON ® 1652 is a SEBScopolymer obtained from Kraton Polymers, Houston, TX. ¹⁰VECTOR ® 4211 isa SIS from Dexco Polymers, Houston, TX.

Examples 20-24 and 5, 7, 8, 13, and 16 and some commercial polymers asshown in Table 11 above were formulated into pressure sensitiveadhesives (PSA) by the addition of a tackifier and Kaydol oil. Theresulting viscosity of the formulated system was low as compared to thebase polymer. The viscosity of the PSA was measured to indicate itsability to be applied easily onto a substrate. Preferred ranges ofviscosity for the formulated adhesive are from about 500 to about300,000 cP at 350° F. (177° C.) as measured by Brookfield viscosity,more preferably from about 500 to about 150,000 cP, and most preferablyfrom about 500 to about 50,000 cP. Especially preferred are higher flowmulti-block samples (i.e., ˜10 I₂) which yielded especially lowviscosities of from about 1 to about 11,000 cP at 350° F. depending onthe percentage and type of tackifier and oil used.

FIG. 8 shows plots of storage modulus versus temperature for Examples32-33, as compared to comparative Examples L and M. FIG. 9 shows plotsof storage modulus versus temperature for Examples 34-36, as compared tocomparative Examples N, P, and Q.

Coating of Pressure Sensitive Adhesive Samples

All pressure sensitive adhesive samples were coated as hot melts by handonto 2 mil (50.8 microns) Mylar film using a P.G. & T. CO. #1 applicator(stainless steel wet film applicator available from the Paul N. GardnerCompany, Pompano Beach, Fla.) which was preheated to the adhesiveapplication temperature of 177° C. (350° F.). Just prior to drawing downthe adhesives onto the Mylar film, the coating edge of the applicatorwas heated briefly over a Bunsen burner to help facilitate obtaining assmooth and streak free coating as possible. The adhesive coat weight forall samples was 25 gsm (grams per square meter).

Coating of Hot Melt Adhesive Samples

All hot melt adhesive samples were coated as hot melts by hand ontoKraft paper (Inland board stock) using a P.G. & T. CO. #1 applicator(stainless steel wet film applicator available from the Paul N. GardnerCompany) which was preheated to the adhesive application temperature of177° C. (350° F.). If the viscosity of the formulation was too high toyield an easily flowable formulation, the temperature was raised to 191°C. (375° F.). These samples were prepared using two sheets of 40 poundKraft paper, each of about 6×12 inches (152×305 mm) dimensions. On thebottom sheet, lengthwise and separated by a gap of 1 inch (25 mm) wereadhered in parallel fashion two 1.75 or 2 inches (45 or 51 mm) widestrips of a one sided, pressure-sensitive tape such as masking tape. Theadhesive sample to be tested was heated to 177° C. (350° F.) anddrizzled in an even manner down the center of the gap formed between thetape strips. Then, before the adhesive could unduly thicken, two glassrods (applicators), one rod riding immediately upon the tapes andshimmed on each side of the gap with a strip of the same tape followedby the second rod and (between the two rods) the second sheet of paper,were slid down the length of the sheets. This was done in a fashion suchthat the first rod evenly spread the adhesive in the gap between thetape strips and the second rod evenly compressed the second sheet overthe top of the gap and on top of the tape strips. Note that just priorto drawing down the adhesives onto the Kraft paper, the coating edge ofthe applicator was heated briefly over a Bunsen burner to helpfacilitate obtaining as smooth and streak free coating as possible. Thusa single 1 inch wide strip of sample adhesive was created, between thetwo tape strips, and bonding the paper sheets. The sheets so bonded werecut crosswise into strips of width 1 inch and length of about 3 inches,each strip having a 1×1 inch (25×25 mm) adhesive sample bond in thecenter. The adhesive coat weight for all samples was 25 grams per squaremeter.

Adhesive Test Procedures

Brookfield Viscosity

Melt viscosity is determined by ASTM D3236, which is incorporated hereinby reference, using a Brookfield Laboratories DVII+ Viscometer equippedwith disposable aluminum sample chambers. In general, a SC-31 spindle isused, suitable for measuring viscosities in the range of from 30 to100,000 centipoise (cP). If the viscosity is outside this range, analternate spindle should be used which is suitable for the viscosity ofthe polymer. A cutting blade is employed to cut samples into piecessmall enough to fit into the 1 inch wide, 5 inches long samples chamber.The disposable tube is charged with 8-9 grams of polymer. The sample isplaced in the chamber, which is in turn inserted into a BrookfieldThermosel and locked into place with bent needle-nose pliers. The samplechamber has a notch on the bottom that fits in the bottom of theBrookfield Thermosel to ensure that the chamber is not allowed to turnwhen the spindle is inserted and spinning. The sample is heated to thedesired temperature (177° C./350° F.). The viscometer apparatus islowered and the spindle submerged into the sample chamber. Lowering iscontinued until brackets on the viscometer align on the Thermosel. Theviscometer is turned on, and set to a shear rate which leads to a torquereading in the range of 40 to 70 percent. Readings are taken everyminute for about 15 minutes, or until the values stabilize, and then thefinal reading is recorded. The Brookfield viscosity test results arelisted in Table 11 above.

Solid State DMA of Adhesive Formulations

Dynamic Mechanical Analysis (DMA) of pressure sensitive formulatedadhesives was measured on an ARES controlled strain rheometer (TAinstruments) equipped with 7.9 mm parallel plates. The sample wassubjected to successive temperature steps from −70° C. to 200° C. (3° C.per step). At each temperature the rheological properties (storagemodulus G′, loss modulus G″, complex viscosity η*, tan delta or ratio ofG″/G″, etc.) were measured at an angular frequency of 1 rad/s. Otherparameters used were a soak time of 30 seconds, an initial strain of0.1%, a delay before test of 2 minutes, autotension (in compression mode(applying constant static force) with an initial static force of 1 g, anautotension sensitivity of 5 g (sample modulus less than or equal to5×10⁶ dynes/cm²), and autostrain (maximum applied strain of 5%, torquerange=150-1500 g-cm, strain adjustment=50%).

Some of the samples could be molded into plaques while others, whichwere too sticky, could not be molded. Samples that could be molded werepressed at 177° C. (350° F.) for about three minutes into a plaque usingTeflon shims. The desired thickness for the plaque was about 2.5 mm. (Ifthe sample could not be pressed then a small portion was placed directlyon the bottom plate (7.9 mm parallel plate). After molding, a 5/16″punch was used to remove a test specimen from the plaque. The specimenwas loaded into the ARES rheometer fitted with 7.9 mm parallel plates.The sample was placed on the bottom plate at about room temperature. Thetop plate was brought down until it touched the sample and created anormal force of 50 to 300 g. Good contact was made on both the bottomand top plates. The temperature control chamber was closed and thesample was heated to 150° C. to 170° C. and allowed to equilibrate atthe temperature for about 5 minutes. The sample was compressed to 2 mmthickness. The chamber was opened and excess sample was trimmed. Whilethe sample was still hot, the gap setting was decreased by about 0.1 mmto 1.9 mm. The chamber was closed and the sample was allowed toequilibrate again for about 3 minutes. The temperature was decreased to−70° C. After 3 minutes at −70° C., the sample was tested. The DMA testresults are listed in Table 12 below. The values in Table 12 were chosenat the closest temperature increment to the stated temperature. Thus thevalues could be taken at a maximum of 1.5° C. different than the statedvalue.

TABLE 12 The DMA Testing Data of Adhesives. Tg (° C.) Adhesive G′ (Pa)G′ (Pa) G′ (Pa) G′ (Pa) G′ (Pa) at G′ (0° C.)/ G′ (25° C.)/ Tan δExample at 0° C. at 25° C. at 50° C. at 75° C. 100° C. G′ (50° C.) G′(75° C.) Peak Ex. 32 1.52E+06 8.27E+04 4.94E+04 3.14E+04 2.86E+03 31 3 3Ex. 33 1.73E+06 1.14E+05 4.43E+04 3.20E+04 6.60E+03 39 4 11 Comp. L1.06E+07 1.69E+05 2.45E+04 1.55E+03 NM 433 109 8 Ex. 34 8.62E+064.81E+05 2.03E+05 8.31E+04 3.28E+04 42 6 9 Ex. 35 6.24E+06 2.70E+059.88E+04 6.03E+04 1.79E+04 63 4 8 Comp. M 8.86E+06 1.49E+05 1.85E+044.08E+02 NM 479 365 9 Ex. 36 4.52E+06 1.44E+05 5.90E+04 3.95E+046.27E+03 77 4 9 Comp. N 4.34E+06 8.25E+04 7.36E+03 7.84E+01 NM 590 10529 Comp. O 1.75E+07 6.44E+05 1.41E+05 4.72E+04 3.08E+04 124 14 8 Comp. P6.74E+05 9.66E+04 1.00E+05 7.56E+04 9.60E+03 7 1 −1 Comp. Q 8.45E+051.20E+04 1.10E+04 1.24E+04 4.45E+03 77 1 9 Ex. 37 1.08E+07 2.37E+055.41E+04 3.28E+04 1.16E+03 200 7 14 Comp. R 9.09E+06 1.02E+05 5.66E+031.35E+02 NM 1606 758 14 Comp. S 1.90E+07 5.62E+05 8.83E+04 3.52E+043.38E+04 215 16 12 Ex. 38 3.78E+04 7.30E+03 4.99E+03 3.62E+03 NM 8 2 12Comp. T 3.40E+06 3.73E+04 1.55E+03 NM NM 2188 NA 9 Comp. U 3.27E+071.69E+06 5.16E+05 2.46E+05 1.25E+05 63 7 8 Ex. 39 2.21E+04 2.12E+038.99E+02 1.02E+03 NM 25 2 15 Comp. V 1.31E+06 6.94E+03 1.63E+02 3.00E+01NM 8037 231 8 Comp. W 1.74E+07 5.34E+05 8.54E+04 3.59E+04 3.26E+04 20415 12 Ex. 40 NM 2.11E+04 1.22E+04 6.11E+03 8.40E+01 NA 3 NM Ex. 421.02E+05 4.54E+04 2.94E+04 1.90E+04 2.58E+02 3 2 −24 Ex. 43 8.43E+038.68E+02 5.13E+02 2.72E+02 NM 16 3 11 Ex. 44 NM 1.89E+04 1.00E+045.74E+03 2.14E+03 NA 3 NM Ex. 45 9.19E+05 3.16E+05 2.15E+05 1.41E+051.97E+04 4 2 −16 Ex. 46 NM 2.51E+02 NM NM NM NA NA NM Ex. 47 1.40E+063.10E+05 2.07E+05 1.35E+05 1.90E+04 7 2 −10 Ex. 48 2.91E+05 9.51E+046.03E+04 4.01E+04 2.68E+03 5 2 −19 Comp. X 8.78E+04 4.29E+04 3.53E+043.78E+03 NM 2 11 −10 Comp. Y 3.34E+05 1.04E+05 1.54E+04 1.50E+031.00E+02 22 69 −13 Ex. 49 9.44E+04 3.97E+04 2.70E+04 1.85E+04 5.21E+02 42 −19 Ex. 50 7.48E+05 1.33E+05 8.67E+04 5.06E+04 3.11E+03 9 3 −8 Ex. 51NM 7.08E+04 3.08E+04 1.52E+04 7.04E+02 NA 5 −1 Ex. 52 5.30E+05 1.75E+051.18E+05 7.36E+04 5.12E+03 4 2 −16 Ex. 54 6.61E+05 6.37E+04 2.44E+042.52E+03 3.85E+02 27 25 60 Ex. 55 1.77E+08 1.31E+07 9.53E+05 1.30E+051.93E+04 186 101 44 Ex. 56 5.48E+06 8.75E+05 5.03E+05 3.26E+05 9.46E+0411 3 −7 Ex. 57 8.13E+06 1.03E+06 4.95E+05 2.95E+05 8.48E+04 16 3 −4 Ex.58 8.36E+05 5.20E+05 3.37E+05 2.34E+05 5.75E+04 2 2 42 Ex. 59 5.05E+053.00E+05 1.91E+05 1.31E+05 1.75E+04 3 2 42 Comp. Z 7.71E+05 2.63E+041.96E+04 1.69E+04 4.15E+03 39 2 5 Comp. AA 9.91E+06 2.06E+05 4.31E+044.60E+03 5.88E+02 230 45 8 Comp. AB 2.01E+05 2.93E+05 1.06E+05 3.05E+044.00E+02 2 10 18 Ex. 60 1.78E+07 7.99E+05 2.76E+05 1.90E+05 1.08E+05 644 14 Ex. 61 1.67E+07 5.40E+05 2.23E+05 1.53E+05 3.78E+04 75 4 14 Ex. 621.37E+07 2.69E+05 1.22E+05 6.57E+04 7.34E+03 112 4 11 Ex. 63 1.16E+071.02E+06 4.49E+05 2.75E+05 1.56E+05 26 4 1 Ex. 64 3.86E+06 4.10E+052.55E+05 2.06E+05 8.54E+04 15 2 1 Comp. AC 1.41E+05 1.15E+05 9.48E+041.27E+04 NM 1 9 −30 Comp. AD 3.51E+05 1.62E+05 2.22E+04 1.44E+032.81E+02 16 113 −33 Comp. AE 5.37E+05 2.73E+05 1.34E+05 3.01E+041.42E+02 4 9 −32 Ex. 65 1.05E+06 6.24E+05 4.25E+05 2.75E+05 1.24E+05 2 2−37 Ex. 66 4.40E+05 2.77E+05 1.90E+05 1.34E+05 3.47E+03 2 2 −36 Ex. 676.34E+05 3.99E+05 2.86E+05 1.89E+05 6.31E+04 2 2 −37 Ex. 68 2.80E+051.49E+05 9.92E+04 5.04E+04 2.10E+03 3 3 −36 Ex. 69 5.47E+05 3.67E+052.77E+05 1.62E+05 3.20E+04 2 2 −38 Note that “NM” stands for “notmeasured.”

The storage modulus data (G′) of the adhesive compositions at varioustemperatures and their ratios, as well as the peak in the tan deltacurve or T_(g), are tabulated in Table 12 as they are often used as ameans to characterize the goodness of a pressure sensitive adhesive (D.Satas (Ed.) Handbook of Pressure Sensitive Adhesive Technology, Chapter8, S. G. Chu, “Viscoelastic Properties of Pressure Sensitive Adhesives”,p. 158-203, Van Nostrand Reinhold (1989). Adhesive properties weremeasured on selected samples and include SAFT, peel to stainless steel(SS) and polypropylene (PP), loop tack, and room temperature (RT) shear.The storage modulus (G′) of some adhesive examples are shown in FIGS. 8and 9.

In some embodiments, the storage moduli G′ of the adhesive compositionsat 25° C. are from about 1×10³ to about 1×10⁶ Pa, from about 2×10³ toabout 5×10⁵ Pa, or from about 1×10⁴ to about 5×10⁵ Pa.

In other embodiments, the adhesive compositions have a relatively flatG′ curve in the general temperature range of interest of use (i.e., from0 to 75° C.), indicating the G′ and other properties related to G′ havea relatively small temperature dependence. In further embodiments, theG′ of some PSA's (e.g., Examples 32-69) made from interpolymersdisclosed herein have a relatively flat G′ curve in the temperaturerange from 0 to 75° C. which is similar to those PSA's (e.g.,Comparatives P, Q, X, Z and AC) made from conventional block copolymers(KRATON® and VECTOR®). In particular embodiments, the ranges of storagemodulus ratio G′ (25° C.)/G′ (75° C.) are from about 1:1 to about 110:1,from about 1:1 to about 75:1, from about 1:1 to about 25:1, from about1:1 to about 20:1, from about 1:1 to about 15:1, from about 1:1 to about10:1, from about 1:1 to about 9:1, from about 1:1 to about 8:1, fromabout 1:1 to about 7:1, from about 1:1 to about 6:1, from about 1:1 toabout 5:1, or from about 1:1 to about 4:1.

Shear Adhesion Failure Temperature (SAFT)

Shear adhesion failure temperature (SAFT) of each sample was measuredaccording to ASTM D 4498 with a 500 gram weight in the shear mode. Thetests were started at room temperature (25° C./77° F.) and the oventemperature was ramped at an average rate of 0.5° C./minute. Thetemperature at which the specimen failed was recorded. This measurementwas used as an indication of the heat resistance of the compositionwhich is important for shipping. The SAFT test results are listed inTable 13 below.

Peel Adhesion Failure Temperature (PAFT)

Peel adhesion failure temperature (PAFT) was tested according to ASTM D4498 with a 100 gram weight in the peel mode. The tests were started atroom temperature (25° C./77° F.) and the temperature was increased at anaverage rate of 0.5° C./minute. The PAFT test results are listed inTable 13 below.

180 Degree Peel Adhesion to Stainless Steel and Polypropylene

The 180 degree peel adhesion to stainless steel and also topolypropylene test panels was tested according to the Pressure SensitiveTape Council PSTC-1 method with a peel rate of 12″/minute. The 180degree peel adhesion to stainless steel (SS) and polypropylene (PP)substrates are listed in Table 13 below.

Loop Tack

The loop tack was tested by method ASTM 6195-03 test method-A, which isincorporated herein by reference. The loop tack test results are listedin Table 13 below.

RT Shear

Static shear at room temperature (RT) was tested using a 1 kg weight anda modified ASTM-D-4498, which is incorporated herein by reference. Thestatic shear at room temperature test results are listed in Table 13below.

TABLE 13 The SAFT, 180 Degree Peel Adhesion To Stainless Steel (SS) andPolypropylene (PP), Loop Tack, And Room Temperature (RT) Shear TestResults of PSA Examples. Mean Mean Peel Mean Peel Loop RT PSA SAFT SAFTAdhesion Adhesion Tack Shear Example (° F.) (° C.) to SS (lb) to PP (lb)(lb) (min.) Ex. 32 129 54 3.2 0.2 NM NM Ex. 33 111 44 1.6 0.4 NM NMComp. L 137 58 0.4 0.1 NM NM Ex. 34 147 64 3 3.2 NM NM Ex. 35 147 64 0.80 NM NM Comp. M 137 58 1.4 1.1 NM NM Ex. 36 117 47 4.1 4.2 0.9 NM Comp.N 129 54 4.4 4.2 1.9 NM Comp. O 115 46 3.4 4.1 0.9 NM Comp. P 191 88 4.93.6 NM NM Comp. Q 104 40 6.6 6.5 6.3 NM Ex. 37 153 67 3.2 0.8 0 NM Comp.R 132 56 3 2.8 0 NM Comp. S 140 60 0.8 0.7 0 NM Ex. 38 104 40 5.8 4.19.5 NM Comp. T 125 52 7 6.7 0.9 NM Comp. U 101 38 2.4 1.8 3.9 NM Ex. 39131 55 6.9 6.9 0.5 NM Comp. V 116 47 6.8 5.7 2.5 NM Comp. W 99 37 3.63.1 6.3 NM Comp. Z 180 82 6.9 NM NM >5000 Comp. AA 153 67 0.33 NMNM >5000 Comp. AB 134 57 0.27 NM NM >5000 Ex. 60 130 54 0.24 NM NM >5000Comp. AC 155 68 0.2 NM NM >5000 Comp. AD 87 31 <0.1 NM NM <1 Comp. AE 8127 <0.1 NM NM <1 Ex. 65 89 32 <0.1 NM NM 2

In some embodiments, the SAFT of the adhesive compositions are greaterthan or equal to 90° F., greater than or equal to 110° F., greater thanor equal to 130° F. or greater than or equal to 150° F. In general, theadhesive compositions having a high SAFT can be used at hightemperatures.

In other embodiments, the 180 degree peel adhesion of the adhesivecompositions to SS are greater than 0.1 lb, greater than 1.5 lb, orgreater than 3 lb. Examples 37 and 39 show good combination of high SAFTand high peel adhesion to SS.

In other embodiments, the 180 degree peel adhesion of the adhesivecompositions to polypropylene (PP) are greater than 0.1 lb, greater than1.5 lb, or greater than 3 lb. Example 39 shows good combination of highSAFT and high peel adhesion to SS as well as high peel adhesion to PP.This peel adhesion to PP is much higher than that of the KRATON®-basedformulation (Comparative Example P*) with a slightly differentformulation.

In other embodiments, the loop tack of the adhesive compositions aregreater than 0.5 lb, greater than 1 lb, or greater than 2 lb. Example 38has a surprisingly high loop tack of 9.5 lb, greater than any otheradhesive examples tested.

Table 14 shows the density, Brookfield viscosity, M_(w), M_(n),M_(w)/M_(n) ratio, heat of fusion, T_(m), T_(m2), T_(c), T_(c2), tensilestrength and % elongation at break of Examples 25-26, AFFINITY® GA 1950and AFFINITY® GA 1900. The tests have been described earlier. Example 26has a density, Brookfield viscosity, M_(w), M_(n), and M_(w)/M_(n) ratiosimilar to those of AFFINITY® GA 1950. Similarly, Example 25 has adensity, Brookfield viscosity, M_(w), M_(n), and M_(w)/M_(n) ratiosimilar to those of AFFINITY® GA 1900. AFFINITY® GA 1950 and AFFINITY®GA 1900 are produced using a single site catalyst. Having similar valuesin density, Brookfield viscosity, M_(w), M_(n), or M_(w)/M_(n) ratio,Examples 25-26 show much higher melting temperatures (110° C.) than thecorresponding comparative examples, i.e., AFFINITY® GA 1950 (72° C.) andAFFINITY® GA 1900 (67° C.).

Examples 25-26, AFFINITY® GA 1950 and AFFINITY® GA 1900 were formulatedinto hot melt adhesives by the addition of a tackifier and a waxaccording to the formulations listed in Table 15. The resultantadhesives (i.e., Examples 66-67 and Comparatives AF and AG) were testedfor Brookfield viscosity, PAFT, SAFT, and fiber tear. The Brookfieldviscosity, PAFT, SAFT have been described earlier. The percent fibertear test is described below. The Brookfield viscosity, PAFT, SAFT, andfiber tear test results are listed in Table 15.

Percent Fiber Tear

The percent fiber tear test was conducted with a corrugated board stockaccording to a standard industry test. The adhesive sample to be testedwas heated to 177° C./350° F. and was applied on the board stock cutinto 1×3 inch (25×76 mm) rectangular sheets with the corrugated flutesrunning lengthwise. The adhesive sample was applied, running lengthwise,as about a 5 mm (i.e., 0.2 inch) wide strip and could be drawn down witha spatula or hot melt applicator. Next a second strip was applied within2 seconds and held, with moderate pressure, for 5 seconds to laminate.Laminated samples were conditioned for at least 24 hours at temperatures(i.e., 0, 35, 77 and 140° F.) selected for testing. For each selectedtemperature, a laminated sheet was held near one corner and using aspatula, one corner of one of the laminated sheets was folded back toform a hand hold. With the laminate held as near as possible to thesource of heating or cooling in order to maintain the conditioningtemperature, the folded corner was manually pulled as rapidly aspossible at roughly a 45 to 90 degree angle relative to each sheet'slengthwise axis to tear the adhesive bond. The percent of torn fiber wasestimated (fiber tear or FT) in 25% increments: i.e., 0%, 25%, 50%, 75%and 100%. Unless otherwise stated, the FT test was repeated on fivereplicate samples and the average of these five runs was reported.

In some embodiments, the PAFT of the hot melt adhesive compositions isgreater than 130° F., greater than 140° F., or greater than 150° F. Inother embodiments, the SAFT of the hot melt adhesive compositions isgreater 180° F., greater than 190° F., or greater than 200° F.

In some embodiments, the rating of the Fiber Tear of the hot meltadhesive compositions is 100% at 77° F.-140° F. In other embodiments,the rating of the Fiber Tear of the hot melt adhesive compositions is50% or greater at 35° F. and 100% at 35° F.-140° F. In furtherembodiments, the rating of the Fiber Tear of the hot melt adhesivecompositions is 50% or greater at 0° F. and 100% at 35° F.-140° F.

Example 66 shows good high temperature PAFT and SAFT, as well as fibertear over a wide temperature range. Therefore, Example 66 may performwell over a wide temperature range.

TABLE 14 The Properties of Examples 25-26, AFFINITY ® GA 1950 andAFFINITY ® GA 1900. Brookfield Heat of Tensile Density Viscosity @ M_(w)M_(n) Fusion T_(m2) T_(c) T_(c2) Strength Elongation Sample (g/cm³) 177°C. (cP) (g/mol) (g/mol) M_(w)/M_(n) (J/g) T_(m) (° C.) (° C.) (° C.) (°C.) (MPa) at Break (%) Ex. 26 0.8771 15,757 22,400 9,720 2.3 60 110 9695 20.3 2.1 190 AFFINITY ® 0.8755 15,237 22,500 10,100 2.2 64 72 NA 5333 2.3 262 GA 1950¹ Ex. 25 0.8707 7,168 19,800 8,810 2.2 14 110 92 9510.4 1.2 72 AFFINITY ® 0.8714 7.873 19,500 9,020 2.2 57 67 NA 50 30 1.7137 GA 1900² NM: Not Measured NA: Not Applicable ¹AFFINITY ® GA 1950 isa polyolefin plastomer obtained from The Dow Chemical Co., Midland, MI.²AFFINITY ® GA 1900 is a polyolefin plastomer obtained from The DowChemical Co., Midland, MI.

TABLE 15 The Formulations and Properties of Hot Melt Adhesives fromExamples 25-26, AFFINITY ® GA 1950 and AFFINITY ® GA 1900. Wax⁴ Hot Melt(Paraflint Brookfield Adhesive Polymer Tackifier³ H1) Viscosity PAFTPAFT SAFT SAFT FT FT FT FT Example⁵ Polymer ( ) wt % wt % wt % 177° C.(cP) (° F.) (° C.) (° F.) (° C.) 0° F. 35° F. 77° F. 140° F. Ex. 66 Ex.26 34.5 35 30 15,757 165 74 211 99 50 100 100 100 Comp. AF AFFINITY ®34.5 35 30 15,237 160 71 201 94 0 50 100 100 GA 1950¹ Ex. 67 Ex. 25 29.535 35 7,168 149 65 195 91 0 0 100 100 Comp. AFFINITY ® 29.5 35 35 7.873156 69 204 96 0 0 100 100 AG GA 1900² ¹AFFINITY ® GA 1950 is apolyolefin plastomer obtained from The Dow Chemical Co., Midland, MI.²AFFINITY ® GA 1900 is a polyolefin plastomer obtained from The DowChemical Co., Midland, MI. ³The tackifier was EASTOTAC ® H142R obtainedfrom Eastman Company, Kingsport, Tennessee. ⁴The wax was PARAFLINT ® H1,a synthetic wax having a softening point of 104° C. ⁵All the samplescontained 0.5 wt % IRGANOX ® I1010, a hindered phenolic antioxidant fromCiba Specialty Chemicals, Tarrytown, NY.

Hot Melt Adhesives Examples 68-75

Interpolymers of Examples 22, 27-31, 31a and 31b were used inpreparation of hot melt adhesives and their potential for use inpressure sensitive adhesives (PSA) and graphic arts was evaluated.

First 25/50/25 (polymer/tackifier/oil) blends were prepared with each ofthe eight polymers. The tackifier used was a Hydrogenated DCPD tackifierwith a 100° C. softening point from Eastman Chemical (i.e., EASTOTAC®H-100R). The oil used was a white mineral oil from Sonneborn (i.e.,Kaydol oil). These formulations and results for this series offormulations can be found in Table 16.

The formulated products (Examples 68-75) were made in each case bymelting everything but the polymer together in a one point can in aforced air oven set at 177° C. Once this part of each formulation wasmolten the containers were transferred to a Glas-Col heating mantle setat 177° C. and stirred with a Caframo mixer. The polymer was then addedslowly and mixed until completely smooth.

Coated Sample Preparation

All adhesive samples were coated as hot melts by hand onto 2 mil Mylarfilm using a P.G. & T. CO. #1 applicator which was preheated to theadhesive application temperature of 350° F. Just prior to drawing downthe adhesives onto the Mylar film, the coating edge of the applicatorwas heated briefly over a Bunsen burner to help facilitate obtaining assmooth and streak free coating as possible. The adhesive coat weight forall samples was approximately 25 gsm (gram per square meter).

Tensile and Elongation Sample Preparation

Each product was melted at 120° C. Using a glass rod shimmed to 20 mils,a film of each material was made by pouring a puddle of adhesive ontosilicone release paper and drawing the glass rod over the adhesive.After cooling the films were removed from the silicone release liner andin some cases talced to reduce surface tack. A Carver press and an ASTMD-638-4 die were used to cut dog bones for tensile and elongationtesting.

Bleed Testing @ 120° F.

Coated samples of each formulation were laminated to 20 lb, 88brightness copy paper and placed in an incubator set at 120° F. for twoweeks. At the end of two weeks the back side of the paper was visuallyinspected for oil staining and assigned a number between 1 and 5 with 1being no evidence of staining and 5 being complete staining of the paperstock. Formulation and properties for adhesive Examples 68-75 aresummarized in Table 16.

Resistance to Plasticizer Migration at 120° F.

Coated samples of each formulation were laminated to 25 mil embossedvinyl fabric and conditioned at 120 F for a period of one week. At theend of one week, the laminates were removed from the incubator andallowed to cool back to room temperature. The coated films were thenpeeled off the vinyl fabric and visually inspected for evidence ofcontamination of the adhesive due to migration of plasticizer.Contamination usually results in softening of the adhesive and in severecases the total loss of cohesive strength. The adhesives were assigned anumber between 1 and 5 with 1 being no evidence of migration of theplasticizer into the adhesive and 5 being severe migration resulting intotal loss of cohesive strength.

TABLE 16 Formulation and Properties for Adhesive Examples 68-75 ExampleExample Example Example Example Example Example Example Ingredients 6869 70 71 72 73 74 75 Polymer Ex. 27 25% Polymer Ex. 28 25% Polymer Ex.29 25% Polymer Ex. 30 25% Polymer Ex. 31 25% Polymer Ex. 22 25% PolymerEx. 31a 25% Polymer Ex. 31b 25% Kaydol oil 25% 25% 25% 25% 25% 25% 25%25% EASTOTAC ® H-100R 50% 50% 50% 50% 50% 50% 50% 50% IRGANOX ® 10100.5%  0.5%  0.5%  0.5%  0.5%  0.5%  0.5%  0.5%  Tests Viscosity @ 350 F.(cps) NA 97500 86000 18400 17500 8450 6880 3100 SAFT¹ (F.) 155 139 105159 131 127 130 125 SAFT² (F.) 160 134 129 127 125 Loop Tack¹ (pli) 1.90.5 1.3 3.3 0.3 0.4 0.4 1.6 Loop Tack² (pli) 4.1 0.7 1.3 1.2 4 180degree peel to SS¹ 4.1 2.7 0.4 6.0 4.2 4.1 3.8 6.2 (pli) Aged peel toSS*^(, 1) (pli) 5.08 0.44 0.6 6.05 0.92 2.9 0.57 5.9 180 degree peel toSS² 1.9 0.3 0.4 2.6 4.1 (pli) 180 degree peel to PE² 1.3 0.3 0.1 0.2 0.3(¼″ thick PE) 180 degree peel to PP² 2.8 1.7 1.9 0.7 2.7 (¼″ thick rigidPP) Bleed testing @ 120 F. for 1 4 5 1 4 4 3 3 one week 3 days on Vinylat 120 F. 2 3 *Measured after aging films at 120 F. for two weeks andequilibrating back to room temperature before testing. ¹When coated ashot melt by hand. ²When machine coated using an Acumeter bench top slotdie coater.

Hot Melt Adhesives Examples 76-80

Based on the results of the polymer screening formulations (Examples68-75), polymer of Example 30 was chosen for further adhesiveformulations of Examples 76-78 designed to study the effect of

-   -   i) increasing the melt point of the tackifier and    -   ii) a tackifier with the same melt point that is produced from a        slightly different feed stream.

Various tackifiers were tried in the formulations to see if there wasany difference in compatibility. The tackifiers chosen were a blend ofEASTOTAC® H-130 and H-100 to produce a 115 softening point and ESCOREZ™5415 for the higher softening point tackifiers. ESCOREZ™ 5400 was usedas slightly different feed stream tackifier. The results of theseformulations compared to a high performance, high heat resistance SBCbased PSA (HL-2081 and HL-2053 from H.B. Fuller Company, St. Paul,Minn.) are provided in Table 17.

Polymer Example 31b was selected for testing in two standard GraphicArts formulations (one with a blend of rosin ester and hydrogenated DCPDresin and the other with all DCPD resin). An Industry Standard adhesiveused for comparative purposes (HM-948) and results can also be found inTable 17.

TABLE 17 Formulations and properties for adhesive examples 76-80.Example Example Example Example Example 76 77 78 79 80 HM-948 HL-2081HL-2053 Polymer Example 31 25% 25% 25% Polymer Example 40% 40% 31bKaydol 25% 25% 25% EASTOTAC ® H-100R 25% 35% EASTOTAC ® H-130R 25%ESCOREZ ® 5400 50% ESCOREZ ® 5415 50% 155 paraffin 25% 25% SYLVALITE ®RE- 35% 100L IRGANOX ® 1010 0.5%  0.5%  0.5%  0.5%  0.5%  BrookfieldViscosity 20190 19760 23000 10670 10460 6625 13750 3160 @ 350 F. (cps)SAFT¹ 171 162 175 152 (F.) SAFT² 167 155 169 200 149 (F.) Loop Tack¹ 4.26.4 6.7 6.3 (pli) Loop Tack² 3.2 4 4.4 3.2 6.3 (pli) 180 degree peel to6.4 5.1 5.2 6.9 6.5 stainless steel¹ (pli) Aged peel to 5.9 5 5.7stainless¹ (pli) Loop Tack² (pli) 3.2 4 4.4 6.3 180 degree peel to 6.45.1 5.2 6.5 stainless steel¹ (pli) 180 degree peel to 1.4 1.8 2.7 6.93.7 stainless steel² (pli) 180 degree peel to 1.2 1.2 1.4 2.3 PE² (pli)180 degree peel to 2 2.1 2.6 3.0 PP² (pli) Cold Crack @ 0 Pass Pass Faildegrees F. PAFT Kraft/Kraft 115 130 138 (F.) SAFT Kraft/Kraft 210 211154 (F.) Peak Stress 350 568 605 (psi) ASTM D638-4 Elongation @ break529 152 >1000 (%) ASTM D638-4 Bleed testing at one 1 2 2 3 week 120 F. 3days on vinyl at 2 2 1.5 5 120 F. ¹When coated as hot melt by hand.²When machine coated using an Acumeter bench top slot die coater.

As demonstrated above, in certain embodiments, increasing the melt pointof the tackifier has a positive effect on loop tack and on SAFT. Incertain embodiments, ESCOREZ™ 5400 and 5415 give slightly higher looptack and SAFT as compared to their EASTOTAC® counterparts. In certainembodiments, polymers with less hard segments (blockiness) bleed less,have higher SAFT's and age better than polymers with medium to highlevels of blockiness. The formulations show good aged properties. Theadhesive formulations based on polymer Example 30 have properties closeto and in certain embodiments, superior to HL-2081 which is consideredto be a high performance, high heat resistance SIS based PSA.

The two graphic arts products based on polymer of Example 31b arecomparable to the industry standard HM-948. In certain embodiments, thegraphic art formulations provided herein have superior low temperatureflexibility. In certain embodiments, the low temperature flexibility isuseful in making freezer grade adhesives. In certain embodiments, thesepolymers find utility where plasticizer resistance is required (likebonding vinyl substrates).

Elastic Attachment Test Procedure

For the examples in Table 18, 2000 gram batches of each adhesive wereprepared in a high shear sigma blade mixer set at 325° F. The adhesiveswere then transferred to a melter set at 325° F. and applied with aNordson spiral spray system onto three strands of Lycra thread (Decitex940 type 151) using the method described in U.S. Pat. No. 4,842,666.After equilibrating to room temperature the laminations were thenstretched to 95% of full extension and fastened to a rigid piece ofcardboard. The ends of the elastic were then cut through thepolyethylene film and the test board placed in an incubator set at 100°F. After a period of four hours the test board was removed and thepercent creep calculated using the formula: Initial length minus finallength divided by initial length times 100. This method is describedmore fully in U.S. Pat. No. 6,531,544. In Table 18, Comparative ExampleAF and HL-8128 (from H. B. Fuller Company, St. Paul, Minn.) are used tocompare to the construction adhesive Examples 81-83 and HL-1486 (from H.B. Fuller Company, St. Paul, Minn.) is used to compare to the elasticattachment Examples 84 and 85.

Pressure sensitive adhesives based on Polymer Examples 27 and 30 aremore resistant to bleeding at 120° F. for one week than the standard SBCbased adhesive HL-2053. Examples 76-78 were less affected by plasticizermigration when placed in contact with 25 mil vinyl fabric for three daysat 120° F. than the standard SBC based adhesive HL-2053. Examples 76-78maintained good adhesion to the vinyl and only suffered slight loss ofcohesive strength. The HL-2053 SBC based adhesive lost all of itscohesive strength and became extremely gummy after only one day in thistest.

Construction Adhesive Bond Preparation Substrates and Equipment

-   -   Clopay DH-203 1.0 mil embossed polyethylene    -   BBA Style 717D (16.9 gsm) spunbond nonwoven    -   Acumeter model 3900 10 PG melter    -   Nordson model CWEO5-M2RCXE Spray System    -   Nordson single module 0.018 spiral spray nozzle    -   May Coating CLS-300 coater laminator

A 2000 gm sample of each adhesive formulation was prepared in a sigmablade high shear mixer set at 325° F. The products were then transferredto an Acumeter Model 3900 10 PG melter for spiral spray applicationbetween polyethylene film and nonwoven fabric. All of the adhesives wereapplied onto the polyethylene backsheet and then laminated using 30 psinip pressure to the nonwoven fabric. The web speed was adjusted based onthe adhesive through put to obtain a coat weight of 6.2 gsm atapproximately 500 ft/minute. The air flow and nozzle height was adjustedfor each adhesive until the best possible 20 mm wide spiral pattern wasobtained. The spiral patterns were then rated on a 1-10 scale with 10being a perfectly concentric pattern with good edge control and 1 beinga very poor spiral pattern that appears to look more like melt blownthan spiral. A SIS based industry standard adhesives (HL-8128) alongwith Comparative AF based are included with the inventive samples.

Spiral Spray Bond Testing

The poly/nonwoven laminations were peeled apart using an I-Mass slippeel tester set at a peel rate if 12 inches/minute and the average forcerecorded over a 20 second time period. For each product 6 constructswere peeled and the average of the 6 averages recorded along with thestandard deviation. Initial peel means peeled at room temperature afterequilibrating at room temperature for 24 hours. Aged peel means agingthe bonds at room temperature for 24 hours then 50° C. for two weeks andthen equilibrating at room temperature for 24 hours and then peeling.The 37° C. peel means conditioning the bonds for 24 hours at RT and thenplacing the constructs in a chamber set at 37° C. for one hour andpeeling them at 37° C.

TABLE 18 Formulations and properties for adhesive examples 81-85.Example Comp. Example Example HL- Example 81 Example 82 83 AF HL-8128 8485 1486 Polymer Example 30 20 5 20 Polymer Example 31b 20 25 AffinityGA-1900 55 60 Kaydol oil 20 25 25 15 EASTOTAC ® H-100R 60 55 55 60EASTOTAC ® H-130R 40 ESCOREZ ® 5637 40 IRGANOX ® 1010 0.5 0.5 0.5 0.50.5 0.5 Brookfield Viscosity at 300° F. (cP) 4850 20000 15000 7125 305020000 12200 5725 325° F. (cP) 12200 9820 5100 1575 12200 7210 2850 350°F. (cP) 6700 3125 1050 1840 Coat Weight (gsm) 6.2 6.2 6.2 6.2 6.2 30 3030 Pattern Width (mm) 20 20 20 20 20 6.4 6.4 6.4 Target adhesive flow 1818 18 18.9 18 30 30 30 (gms/min) Actual adhesive flow 18.8 20.4 18.818.3 19.4 22 25.2 25 (gms/min) Web speed (ft/min) 522 567 522 485 513366 420 417 Nip Pressure (psi) 30 30 30 30 30 30 30 30 Temperature (C)150 165 165 150 150 150 165 165 Air Pressure (psi) 6 21 10 13 17 6 8 6Nozzle Height (mm) 50 50 50 35 25 25 25 25 Pump (RPM) 2.4 2.4 2.4 2.22.3 3.2 3.4 3.4 Pump pressure (psi) 194 185 397 388 108 228 282 190Pattern Rating (1-10) 10 7 8 9 9 9 8 9 1 189 281 265 187 240 2 165 191280 199 205 3 183 185 196 189 199 4 213 183 238 230 252 5 200 170 279206 297 6 193 153 409 220 188 Average Initial Peel PE 191 194 278 205230 to Nonwoven (g) 1 100 59 24 2 100 48 21 3 90 60 24 4 88 49 18 5 10052 21 6 87 49 20 Average % Creep 94 53 21 1 120 132 139 92 155 2 122 155402 176 130 3 137 157 161 177 186 4 130 149 153 168 135 5 154 161 569159 178 6 128 165 457 134 190 Average Peel @ 100 F. 132 153 314 151 162PE to Nonwoven (g)

As demonstrated above, Examples 81-83 all exhibited good viscosity,sprayability, pattern rating (10 being the highest) and good average andaged peels at 100° F. as compared to Comparative Example AF and HL-8128,indicating that these materials would be good construction adhesives.Example 83 also showed unexpected and favorable behavior in that thepeel increased with aging at 100° F. indicating that it may be moreadvantageous for use at both room temperature and higher temperaturessuch as 100° F. FIG. 10 is a DSC curve showing the melting behavior ofPolymer Example 30.

TABLE 19 Formulations and properties for adhesive examples 86-87.Example 86 Example 87 Polymer Example 31c 25 Polymer Example 31d 25Kaydol oil 25 25 EASTOTAC ® H-100R 50 50 EASTOTAC ® H-130R IRGANOX ®1010 0.5 0.5 Brookfield Viscosity @ 300 F. (cps) 16900 15800 @ 325 F.(cps) 10500 9400 @ 350 F. (cps) 7310 6880 Loop Tack¹ (Pli) 2.3 2.1 180degree peel to SS¹ (Pli) 2.2 4.1 180 degree peel to PE¹ (Pli) 0.9 1.9180 degree peel to PP¹ (Pli) 2 0.2 SAFT¹ (F.) 147 156 ¹When machinecoated using an Acumeter bench top slot die coater.

Table 19 shows that the adhesive properties using two polymers with thesame overall density but with different melting behavior as shown inFIGS. 11 and 12; with Polymer Example 31c having a broad melting curvewith peaks at 108° C. and 40° C. and Polymer Example 31d having sharpermelting behavior with a melting point at 117° C. Both samples, whenformulated, showed good viscosity, indicating the ability to be appliedat the application temperature of 300° F.-350° F. and good loop tack,peel to various substrates and SAFT.

As demonstrated above, embodiments of the invention provide adhesivecompositions which can be used as a hot melt adhesives or pressuresensitive adhesives. Some adhesives may have relatively high SAFTtemperatures; other adhesives may have relatively high peel adhesion;still other adhesives may have relatively good temperature resistance.Consequently, the adhesives can be used to make labels, tapes, diapers,decals, cases, cartons, or trays, medical devices, bandages, hygieneproducts, etc. They can also be used for book binding. In certainembodiments, the pressure sensitive adhesives are freezer grade pressuresensitive adhesives.

While the invention has been described with respect to a limited numberof embodiments, the specific features of one embodiment should not beattributed to other embodiments of the invention. No single embodimentis representative of all aspects of the invention. In some embodiments,the compositions or methods may include numerous compounds or steps notmentioned herein. In other embodiments, the compositions or methods donot include, or are substantially free of, any compounds or steps notenumerated herein. Variations and modifications from the describedembodiments exist. Finally, any number disclosed herein should beconstrued to mean approximate, regardless of whether the word “about” or“approximately” is used in describing the number. The appended claimsintend to cover all those modifications and variations as falling withinthe scope of the invention.

1. A composition comprising: (i) at least one ethylene/α-olefininterpolymer, wherein the ethylene/α-olefin interpolymer: (a) has aM_(w)/M_(n) from about 1.7 to about 3.5, at least one melting point,T_(m), in degrees Celsius, and a density, d, in grams/cubic centimeter,wherein the numerical values of T_(m) and d correspond to therelationship:T _(m)>−2002.9+4538.5(d)−2422.2(d)², or (b) has a M_(w)/M_(n) from about1.7 to about 3.5, and is characterized by a heat of fusion, ΔH in J/g,and a delta quantity, ΔT, in degrees Celsius, defined as the temperaturedifference between the tallest DSC peak and the tallest CRYSTAF peak,wherein the numerical values of ΔT and ΔH have the followingrelationships:ΔT>−0.1299(ΔH)+62.81 for ΔH greater than zero and up to 130 J/g,ΔT≧48° C. for ΔH greater than 130 J/g,  wherein the CRYSTAF peak isdetermined using at least 5 percent of the cumulative polymer, and ifless than 5 percent of the polymer has an identifiable CRYSTAF peak,then the CRYSTAF temperature is 30° C.; or (c) is characterized by anelastic recovery, Re, in percent at 300 percent strain and 1 cyclemeasured with a compression-molded film of the ethylene/α-olefininterpolymer, and has a density, d, in grams/cubic centimeter, whereinthe numerical values of Re and d satisfy the following relationship whenethylene/α-olefin interpolymer is substantially free of a cross-linkedphase:Re>1481−1629(d); or (d) has a molecular fraction which elutes between40° C. and 130° C. when fractionated using TREF, characterized in thatthe fraction has a molar comonomer content of at least 5 percent higherthan that of a comparable random ethylene interpolymer fraction elutingbetween the same temperatures, wherein said comparable random ethyleneinterpolymer has the same comonomer(s) and has a melt index, density,and molar comonomer content (based on the whole polymer) within 10percent of that of the ethylene/α-olefin interpolymer; or (e) has astorage modulus at 25° C., G′(25° C.), and a storage modulus at 100° C.,G′(100° C.), wherein the ratio of G′(25° C.) to G′(100° C.) is in therange of about 1:1 to about 9:1; and (ii) at least one tackifier,wherein the composition is a pressure sensitive adhesive composition. 2.The composition of claim 1, wherein the ethylene/α-olefin interpolymerhas a M_(w)/M_(n) from about 1.7 to about 3.5, at least one meltingpoint, T_(m), in degrees Celsius, and a density, d, in grams/cubiccentimeter, wherein the numerical values of T_(m) and d correspond tothe relationship:T _(m)≧858.91−1825.3(d)+1112.8(d)².
 3. The composition of claim 1,wherein the ethylene/α-olefin interpolymer has a M_(w)/M_(n) from about1.7 to about 3.5 and is characterized by a heat of fusion, ΔH in J/g,and a delta quantity, ΔT, in degrees Celsius defined as the temperaturedifference between the tallest DSC peak and the tallest CRYSTAF peak,wherein the numerical values of ΔT and ΔH have the followingrelationships:ΔT>−0.1299(ΔH)+62.81 for ΔH greater than zero and up to 130 J/g,ΔT≧48° C. for ΔH greater than 130 J/g, wherein the CRYSTAF peak isdetermined using at least 5 percent of the cumulative polymer, and ifless than 5 percent of the polymer has an identifiable CRYSTAF peak,then the CRYSTAF temperature is 30° C.
 4. The composition of claim 1,wherein the ethylene/α-olefin interpolymer is characterized by anelastic recovery, Re, in percent at 300 percent strain and 1 cyclemeasured with a compression-molded film of the ethylene/α-olefininterpolymer, and has a density, d, in grams/cubic centimeter, whereinthe numerical values of Re and d satisfy the following relationship whenethylene/α-olefin interpolymer is substantially free of a cross-linkedphase:Re>1481−1629(d).
 5. The composition of claim 4, wherein the numericalvalues of Re and d satisfy the following relationship:Re>1491−1629(d).
 6. The composition of claim 4, wherein the numericalvalues of Re and d satisfy the following relationship:Re>1501−1629(d).
 7. The composition of claim 4, wherein the numericalvalues of Re and d satisfy the following relationship:Re>1511−1629(d).
 8. A composition comprising: at least oneethylene/α-olefin interpolymer, wherein the ethylene/α-olefininterpolymer has: (a) a molecular fraction which elutes between 40° C.and 130° C. when fractionated using TREF, characterized in that thefraction has a block index of at least 0.5 and up to about 1, or (b) anaverage block index greater than zero and up to about 1.0 and amolecular weight distribution, Mw/Mn, greater than about 1.3 and (ii) atleast one tackifier, wherein the composition is a pressure sensitiveadhesive composition.
 9. The composition of claim 1, wherein theethylene/α-olefin interpolymer has a molecular fraction which elutesbetween 40° C. and 130° C. when fractionated using TREF, characterizedin that the fraction has a molar comonomer content of at least 5 percenthigher than that of a comparable random ethylene interpolymer fractioneluting between the same temperatures, wherein said comparable randomethylene interpolymer has the same comonomer(s) and has a melt index,density, and molar comonomer content (based on the whole polymer) within10 percent of that of the ethylene/α-olefin interpolymer.
 10. Thecomposition of claim 1, wherein the ethylene/α-olefin interpolymer has astorage modulus at 25° C., G′(25° C.), and a storage modulus at 100° C.,G′(100° C.), wherein the ratio of G′(25° C.) to G′(100° C.) is in therange of about 1:1 to about 9:1.
 11. The composition of claim 1, whereinthe α-olefin is styrene, propylene, 1-butene, 1-hexene, 1-octene,4-methyl-1-pentene, norbornene, 1-decene, 1,5-hexadiene, or acombination thereof.
 12. The composition of claim 1, wherein thetackifier is present in the range from about 5% to about 70% by weightof the total composition.
 13. The composition of claim 1, wherein thetackifier has a R&B softening point equal to or greater than 80° C. 14.The composition of claim 1, further comprising an additive selected fromthe group consisting of plasticizers, oils, waxes, antioxidants, UVstabilizers, colorants or pigments, fillers, flow aids, coupling agents,crosslinking agents, surfactants, solvents, and combinations thereof.15. The composition of claim 1, wherein the composition has a shearadhesion failure temperature (SAFT) of at least 32° C.
 16. Thecomposition of claim 1, wherein the composition has a 180° peel adhesionto a polyester substrate of at least about 100 N/dm.
 17. The compositionof claim 1, wherein the composition is a hot melt adhesive and theG′(25° C.) of the hot melt adhesive composition is from about 1×10³ toabout 1×10⁶ Pa.
 18. The composition of claim 17, wherein the ratio ofG′(25° C.) to G′(75° C.) of the hot melt adhesive composition is fromabout 1:1 to about 110:1.
 19. The composition of claim 15, wherein theSAFT of the pressure sensitive adhesive composition is greater than orequal to 12° C.
 20. An article comprising a substrate coated with thecomposition of claim
 1. 21. The article of claim 20, wherein the articleis a medical device, a bandage, or a hygiene article.
 22. Thecomposition of claim 1, wherein the ethylene/α-olefin interpolymer has adensity of about 0.85 to about 0.88 g/cc.
 23. The composition of claim1, wherein the ethylene/α-olefin interpolymer has a density of about0.86 to about 0.875 g/cc.
 24. The composition of claim 1, wherein theethylene/α-olefin interpolymer has a melt index of about 5 to about 50g/10 minutes.
 25. The composition of claim 1, wherein theethylene/α-olefin interpolymer has a melt index of about 10 to about 30g/10 minutes.
 26. The composition of claim 1, wherein theethylene/α-olefin interpolymer is present in a range from about 10% toabut 50% by weight of the total composition.
 27. The composition ofclaim 14, wherein the plasticizer is a mineral oil, liquid polybutene,or a combination thereof.